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Biotransformation of Cinnamic Acid, P-Coumaric Acid, Caffeic

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Biotransformation of Cinnamic Acid, P-Coumaric Acid, Caffeic 100335 (332) Biosci. Biotechnol. Biochem., 74 (9), 100335-1–5, 2010 Biotransformation of Cinnamic Acid, p-Coumaric Acid, Caffeic Acid, and Ferulic Acid by Plant Cell Cultures of Eucalyptus perriniana y Hisashi KATSURAGI,1 Kei SHIMODA,2 Naoji KUBOTA,2 Nobuyoshi NAKAJIMA,3; y Hatsuyuki HAMADA,4 and Hiroki HAMADA5; 1Sunny Health Co., Ltd., Nakajima Bilg., 8-8 Kabuto-cho, Nihonbashi, Chuo-ku, Tokyo 103-0026, Japan 2Department of Chemistry, Faculty of Medicine, Oita University, 1-1 Hasama-machi, Oita 879-5593, Japan 3Industry, Government, and Academic Promotional Center, Regional Cooperative Research Organization, Okayama Prefectural University, Soja, Okayama 719-1197, Japan 4National Institute of Fitness and Sports in Kanoya, 1 Shiromizu-cho, Kagoshima 891-2390, Japan 5Department of Life Science, Faculty of Science, Okayama University of Science, 1-1 Ridai-cho, Kita-ku, Okayama 700-0005, Japan Received April 30, 2010; Accepted May 14, 2010; Online Publication, September 7, 2010 [doi:10.1271/bbb.100335] Biotransformations of phenylpropanoids such as biochemical potential to produce specific secondary cinnamic acid, p-coumaric acid, caffeic acid, and ferulic metabolites.4) The reactions involved in the biotransfor- acid were investigated with plant-cultured cells of mation of organic compounds by plant-cultured cells EucalyptusAdvance perriniana. The plant-cultured View cells of include oxidation, reduction, hydroxylation, esterifica- E. perriniana converted cinnamic acid into cinnamic tion, methylation, isomerization, hydrolysis, and glyco- acid -D-glucopyranosyl ester, p-coumaric acid, and sylation. Hydroxylation and glycosylation are character- 4-O- -D-glucopyranosylcoumaric acid. p-Coumaric acid istic biotransformation reactions in such cells because was converted into 4-O- -D-glucopyranosylcoumaric hydroxylases and glycosyltransferases are widespread in acid, p-coumaric acid -D-glucopyranosyl ester, 4-O- - plants.5–9) Several studies of the extraction and purifica- D-glucopyranosylcoumaric acid -D-glucopyranosyl tion of phenylpropanoid glycosides from plants have ester, a new compound, caffeic acid, and 3-O- -D- been reported.10–12) Recently, it was reported that glucopyranosylcaffeic acid. On the other hand, incuba- Haematococcus pluvialis biotransformed phenylpropa- tion of caffeic acid with cultured E. perriniana cells noids, viz., ferulic acid and p-coumaric acid, into vanillin, gave 3-O- -D-glucopyranosylcaffeic acid, 3-O-(6-O- -D- vanillic acid, vanillylProofs alcohol, and protocatechuic acid,13) glucopyranosyl)- -D-glucopyranosylcaffeic acid, a new but little attention has been paid to the biotransformation, compound, 3-O- -D-glucopyranosylcaffeic acid -D-glu- such as hydroxylation and glycosylation, and metabolic copyranosyl ester, 4-O- -D-glucopyranosylcaffeic acid, pathway of phenylpropanoids in plant-cultured cells. 4-O- -D-glucopyranosylcaffeic acid -D-glucopyranosyl Here we report the biotransformation of cinnamic acid, ester, ferulic acid, and 4-O- -D-glucopyranosylferulic p-coumaric acid, caffeic acid, and ferulic acid by plant- acid. 4-O- -D-Glucopyranosylferulic acid, ferulic acid cultured cells of Eucalyptus perriniana. -D-glucopyranosyl ester, and 4-O- -D-glucopyranosyl- ferulic acid -D-glucopyranosyl ester were isolated from Materials and Methods E. perriniana cells treated with ferulic acid. Substrates. Cinnamic acid, p-coumaric acid, caffeic acid, and Key words: biotransformation; glycosylation; phenyl- ferulic acid, which were used as substrates, were purchased from propanoid; plant-cultured cells; Eucalyptus Aldrich Chemical (St. Louis, MO). perriniana Cell line and culture conditions. Cultured E. perriniana cells were subcultured at 4-week intervals on solid Murashige and Skoog (MS) Phenylpropanoids, such as cinnamic acid, p-coumaric medium (100 ml in a 300-ml conical flask) containing 3% sucrose, acid, caffeic acid, and ferulic acid, are naturally occur- 10 mmol/l 2,4-dichlorophenoxyacetic acid, and 1% agar (adjusted to ring anti-oxidants that act as effective scavengers of free pH 5.7) at 25 C in the dark. A suspension culture was started by radicals.1–3) It is well known that shikimic acid transferring the cultured cells to 100 ml of liquid medium in a 300-ml is metabolized in plant cells to cinnamic acid and p- conical flask, and this was incubated on a rotary shaker (120 rpm) at 25 C in the dark. Prior to use in this study, part of the callus tissues coumaric acid, which are further converted into caffeic (fr. wt, 40 g) was transplanted to freshly prepared MS medium (100 ml acid and ferulic acid. On the other hand, plant-cultured in a 300-ml conical flask) and grown with continuous shaking for 2 cells are ideal systems for propagating rare plants and for weeks on a rotary shaker (120 rpm). studying the biosynthesis of secondary metabolites. Furthermore, plant-cultured cells are considered to be Biotransformation and purification of products. To a 500-ml flask useful agents for biotransformation reactions due to their containing 200 ml of MS medium and suspension-cultured cells (100 g) y To whom correspondence should be addressed. Nobuyoshi NAKAJIMA, Tel/Fax: +81-866-94-2157; E-mail: [email protected]; Hiroki HAMADA, Tel: +81-86-256-9473; Fax: +81-86-256-8468; E-mail: [email protected] Abbreviations: COSY, correlation spectroscopy; HMBC, heteronuclear multiple-bond correlation; HPLC, high performance liquid chromatog- raphy; HRFABMS, high resolution fast atom bombardment mass spectrometry; NMR, nuclear magnetic resonance; TMS, tetramethylsilane 100335-2 H. KATSURAGI et al. of E. perriniana was added 15 mg of substrate. The cultures were 100 incubated at 25 C for 96 h on a rotary shaker (120 rpm) in the dark. After the incubation period, the cells and medium were separated by filtration with suction. The extraction and purification procedures for the biotransformation products were performed according to previ- ously reported methods.14,15) The yield of products was determined on (%) Yield the basis of the peak area from HPLC, and was expressed as a percentage relative to the total amount of whole reaction products 50 extracted. Analysis of the products. 1H and 13C NMR, H–H COSY, C–H COSY, and HMBC spectra were recorded using a Varian XL-400 spectrometer in pyridine-d5 solution, and the chemical shifts were expressed in (ppm), referring to TMS. The HRFABMS spectra were measured using a JEOL MStation JMS-700 spectrometer (JEOL, Tokyo). The structures of the products were determined on the basis of 48 96 analysis of their HRFABMS, 1H and 13C NMR, H-H COSY, C-H Time (h) COSY, and HMBC spectra. The spectral data of new compounds were as follows: Fig. 1. Time-Course of the Biotransformation of Cinnamic Acid (1) by Cultured Cells of E. perriniana. The substrate, cinnamic acid (1, 15 mg), was incubated with 100 g 4-O- -D-Glucopyranosylcoumaric acid -D-glucopyranosyl ester of E. perriniana suspension cell cultures at 25 C on a rotary shaker (6). HRFABMS m=z ðM þ NaÞþ: Calcd. for C H O Na: 511.1377, 21 28 13 (120 rpm) in the dark. Yields of 1 ( ), 2 ( ), 3 ( ), and 4 ( ) are Found: 511.1382; 1H NMR (400 MHz, pyridine-d ): 4.05–4.67 5 H plotted. (12H, m, H-20,200,30,300,40,400,50,500,60,600), 5.25 (1H, d, J ¼ 7:2 Hz, H-10), 6.11 (1H, d, J ¼ 7:6 Hz, H-100), 6.55 (1H, d, J ¼ 16:0 Hz, H-8), 7.24 (2H, d, J ¼ 8:0 Hz, H-3, 5), 7.51 (1H, d, J ¼ 16:0 Hz, H-7), 7.60 13 O O (2H, d, J ¼ 8:0 Hz, H-2, 6); C NMR (100 MHz, pyridine-d5): C 62.7 (C-60), 63.0 (C-600), 70.7 (C-40), 70.9 (C-400), 74.0 (C-200), 74.1 (C-20), OH OGlc Advance0 00 0 00 View00 77.6 (C-3 ), 77.9 (C-3 ), 78.0 (C-5 ), 78.2 (C-5 ), 99.8 (C-1 ), 102.5 0 (C-1 ), 109.9 (C-3, C-5), 115.0 (C-8), 124.6 (C-2, C-6), 127.5 (C-1), 1 2 (9%) 142.2 (C-7), 155.0 (C-4), 170.2 (C-9). 3-O-(6-O- -D-Glucopyranosyl)- -D-glucopyranosylcaffeic acid (9). þ HRFABMS: m=z ðM þ NaÞ : Calcd. for C21H28O14Na: 527.1428, þ 1 Found: 527.1425 ½M þ Na ; H NMR (400 MHz, pyridine-d5): H 0 00 0 00 0 00 0 00 0 00 4.07–4.57 (12H, m, H-2 ,2 ,3,3 ,4,4 ,5,5 ,6,6 ), 4.99 (1H, d, O O ¼ 00 ¼ 0 J 7:2 Hz, H-1 ), 5.10 (1H, d, J 7:6 Hz, H-1 ), 6.55 (1H, d, OH OH J ¼ 15:6 Hz, H-8), 7.01 (1H, dd, J ¼ 8:0, 1.9 Hz, H-6), 7.08 (1H, d, J ¼ 8:0 Hz, H-5), 7.55 (1H, d, J ¼ 2:0, H-2), 7.70 (1H, d, J ¼ 15:6 Hz, HO GlcO 13 00 0 3 (5%) 4 (2%) H-7); C NMR (100 MHz, pyridine-d5): C 63.0 (C-6 ), 69.3 (C-6 ), Proofs 70.9 (C-40, C-400), 74.2 (C-200), 74.3 (C-20), 77.5, 77.7 (C-30, C-300), 78.1 (C-50, C-500), 99.5 (C-10), 100.0 (C-100), 114.1 (C-8), 114.9 (C-2), 115.5 Fig. 2. Biotransformation Pathway of Cinnamic Acid (1) by Plant- (C-5), 122.0 (C-6), 125.9 (C-1), 145.5 (C-7), 147.0 (C-3), 148.5 (C-4), Cultured Cells of E. perriniana. 165.0 (C-9). time course of the conversion of 1 was followed. As Time-course experiments. Suspension cells (100 g) of E. perriniana Fig. 1 indicates, cinnamic acid (1) was converted into 2 were partitioned to eight flasks containing 200 ml of MS medium.
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