A new hemiterpene glycoside from the ripe tomatoes

Article abstract of DOI:10.1080/14786419.2014.974053

A new hemiterpene glycoside (1) was isolated from ripe tomatoes (the fruit of Lycopersicon esculentum, Solanaceae) along with eight known compounds. The chemical structure of 1 was determined to be 2-methylbutan-1-ol β-d-glucopyranosyl-(1 → 6)-β-d-glucopyranoside, based on spectroscopic data as well as chemical evidence. In addition, the radical-scavenging activities of the isolated compounds on the free radical of 1,1-diphenyl-2-picrylhydrazyl were examined. Among the tested compounds, tryptophan, 4-O-β-d-glucopyranosyl caffeic acid and dihydro-p-coumaryl alcohol γ-O-β-d-glucopyranoside demonstrated 42.0%, 50.1% and 76.0% scavenging activities, respectively, at a concentration of 0.5 mM.

Full text of DOI:10.1080/14786419.2014.974053

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A new hemiterpene glycoside from the
ripe tomatoes
Masateru Onoa, Shin Yasudaa, Yuki Shionoa, Chisato Furusawaa,
Shinya Inabaa, Takayuki Tanakaa, Tsuyoshi Ikedab & Toshihiro
Noharab
a School of Agriculture, Tokai University, Minamiaso 5435, Aso,
Kumamoto 869-1404, Japan
b Faculty of Pharmaceutical Sciences, Sojo University, 4-22-1
Ikeda, Nishi-ku, Kumamoto 860-0082, Japan
Published online: 25 Nov 2014.
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To cite this article: Masateru Ono, Shin Yasuda, Yuki Shiono, Chisato Furusawa, Shinya Inaba,
Takayuki Tanaka, Tsuyoshi Ikeda & Toshihiro Nohara (2015) A new hemiterpene glycoside from the
ripe tomatoes, Natural Product Research: Formerly Natural Product Letters, 29:3, 262-267, DOI:
10.1080/14786419.2014.974053
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Natural Product Research, 2015
Vol. 29, No. 3, 262–267, http://dx.doi.org/10.1080/14786419.2014.974053
A new hemiterpene glycoside from the ripe tomatoes
Masateru Onoa*, Shin Yasudaa, Yuki Shionoa, Chisato Furusawaa, Shinya Inabaa,
Takayuki Tanakaa, Tsuyoshi Ikedab and Toshihiro Noharab
aSchool of Agriculture, Tokai University, Minamiaso 5435, Aso, Kumamoto 869-1404, Japan; bFaculty of
Pharmaceutical Sciences, Sojo University, 4-22-1 Ikeda, Nishi-ku, Kumamoto 860-0082, Japan
(Received 13 July 2014; final version received 30 September 2014)
A new hemiterpene glycoside (1) was isolated from ripe tomatoes (the fruit of
Lycopersicon esculentum, Solanaceae) along with eight known compounds. The
chemical structure of 1 was determined to be 2-methylbutan-1-ol b-D-glucopyranosyl-
(1 ! 6)-b-D-glucopyranoside, based on spectroscopic data as well as chemical
evidence. In addition, the radical-scavenging activities of the isolated compounds on
the free radical of 1,1-diphenyl-2-picrylhydrazyl were examined. Among the tested
compounds, tryptophan, 4-O-b-D-glucopyranosyl caffeic acid and dihydro-p-coumaryl
alcohol g-O-b-D-glucopyranoside demonstrated 42.0%, 50.1% and 76.0% scavenging
activities, respectively, at a concentration of 0.5 mM.
Keywords: Lycopersicon esculentum; tomato; Solanaceae; hemiterpene glycoside;
radical-scavenging effect
1. Introduction
Tomatoes, the fruit of Lycopersicon esculentum (syn. Solanum lycopersicum L., Solanaceae),
are fresh vegetables and are used for cooking and consumption. In previous articles (Fujiwara
et al. 2003, 2004; Ono et al. 2006, 2008, 2010; Ohno et al. 2011), we reported the isolation and
structural elucidation of chemical constituents from ripe tomatoes of some cultivars
(‘Momotaro’, ‘Italian San Marzano’, ‘Chika’ and ‘Komomo’). As part of an ongoing study
regarding the chemical constituents of tomatoes, here we describe the isolation and structural
characterisation of a new hemiterpene glycoside along with eight known compounds from a
cultivar known as ‘Momotarofight’. In addition, the radical-scavenging activity of the isolated
*Corresponding author. Email: mono@agri.u-tokai.ac.jp
q 2014 Taylor & Francis

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263
compounds on the free radical of 1,1-diphenyl-2-picrylhydrazyl (DPPH) is also described
herein.
2. Results and discussion
Smashed ripe tomatoes were successively extracted with H2O and methanol (MeOH). Each
extract was separately subjected to Diaion HP20 column chromatography (Mitsubishi Chemical
Industries Co., Ltd., Tokyo, Japan) and eluted with H2O, MeOH and acetone in turn. The both
MeOH eluates were each concentrated in vacuo and combined to yield fraction 1; this fraction
demonstrated the radical-scavenging activity on DPPH (Ono et al. 2010). Furthermore, fraction
1 was subjected to Sephadex LH-20, silica gel and Chromatorex ODS column chromatography,
as well as HPLC on ODS to yield nine compounds (1–9).
Compound 1 was obtained as an amorphous powder, and exhibited an [M þ Na]þ ion peak at
m/z 435 in the positive ion FAB-MS. The high-resolution (HR)-positive ion FAB-MS suggested
that the molecular formula of 1 was C17H32O11. The 1H NMR spectrum of 1 exhibited signals due
to a primary methyl group [d 0.80 (3H, t, J ¼ 7.5 Hz)], a secondary methyl group [d 0.94 (3H, d,
J ¼ 7.0 Hz)] and two anomeric protons [d 5.15 (1H, d, J ¼ 7.5 Hz), 4.76 (1H, d, J ¼ 8.0 Hz)]. The
13C NMR spectrum of 1 displayed signals due to a methine carbon (d 35.4), an oxygenated
methylene carbon (d 62.8), a methylene carbon (d 26.4) and two methyl carbons (d 16.8, 11.4)
attributed to an aglycone moiety (Agl), along with those due to two hexosyl groups. Accordingly, 1
was determined to be a diglycoside of 2-methylbutan-1-ol. Upon acidic hydrolysis, 1 afforded D-
glucose, as confirmed by optical rotation using chiral detection in HPLC analysis. The 1H and 13
C
NMR signals in 1 were assigned with the aid of 1H–1H COSY, HMQC and HMBC spectra (see
Supplementary material, Table S1, Figure S1). The coupling constants of the signals owing to the
anomeric and methine protons indicated that the glucosyl groups were of the pyranose type and
that glycosidic linkages were of the b-form in the 4C1 conformation. Moreover, the glycosylation
shift (þ7.7 ppm) (Kasai et al. 1977; Seo et al. 1978) at C-6 of the inner glucosyl group (Glc) in the
13C NMR of 1, and the HMBC correlations between C-1 of Agl and H-1 of Glc and between C-6 of
Glc and H-1 of the terminal glucosyl group (Glc0) suggested that the sugar linkages in 1 were
formed at the OH-6 of Glc and the OH-1 of Agl. Consequently, 1 was determined to be 2-
methylbutan-1-ol b-D-glucopyranosyl-(1 ! 6)-b-D-glucopyranoside (Figure 1). However, the
absolute configuration of Agl of 1 could not be assigned.
Compounds 2–9 were identified as corchoionoside C (2) (Yoshikawa et al. 1997),
tryptophan (3), 4-O-b-D-glucopyranosyl caffeic acid (4) (Cui et al. 1990), dihydroconiferyl 4-O-
b-D-glucopyranoside (5) (Higuchi et al. 1977), dihydro-p-coumaryl alcohol g-O-b-D-
glucopyranoside (6) (Cui et al. 1990), tomato-pregnane (7) (Fujiwara et al. 2005), 3-O-b-
lycotetraosyl 3b,16b-dihydroxy-5a-pregnane-20-carboxylic acid 16,22-lactone (8) (Zhou et al.
2006) and esculeoside A (9) (Fujiwara et al. 2003, 2004), respectively, based on comparison to
the spectral data of authentic samples or to those reported previously. Detailed 1H NMR spectral
data of 8 were not previously reported and the some 13C NMR chemical shift assignments of 8
were slightly different (Table S2).
The radical-scavenging activities of 1–9 on DPPH were examined. Compounds 3, 4 and 6
demonstrated 42.0%, 50.1% and 76.0% scavenging activities, respectively, at a concentration of
0.5 mM. However, the activities of the other compounds were less than 10% (data not shown)
(Figure S2). In a parallel experiment, a positive control (Trolox) showed 92.3% of DPPH
radical-scavenging activity.
Notably, increased alkaline phosphatase activity by 2 (Tung et al. 2009), antioxidative and
AGE production inhibition by 3 (Selenge et al. 2013), cytotoxicity by 8 and 9 (Ikeda et al. 2003;
Fujiwara et al. 2004) and inhibition of cholesterol ester accumulation in macrophage owing to 9
(Nohara et al. 2010) were previously reported.

264
M. Ono et al.
O
3
4
1
2
OH
HO
HO
O
H
O
O
O
O
5
OH
OH
NH2
O
O
N
H
Glc
HO
HO
OH
HO
1
3
2
HO
OH
OH
O
O
Lyc
O
7
4
5
6
OCH3
OH
H
Glc
O
O
Glc
Glc
O
Glc
HO
H
N
O
O
O
O HO
HO
HO
OH
O
O
O
O
HO
Lyc:
O
O
HO
O
O
HO
OH
HO
HO
O
HO
OH
Lyc
O
O
Lyc
Glc:
HO
HO
H
H
HO
8
9
Figure 1. Structures of 1–9.
3. Experimental
3.1. General experimental procedures
Optical rotations were performed with a JASCO DIP-1000 KYU digital polarimeter (JASCO Co.,
Tokyo, Japan). MS were recorded on a JEOL JMS-DX-303HF (JEOL Ltd., Tokyo, Japan). 1H and
13C NMR spectra were recorded with a JEOL alpha-500 spectrometer (JEOL Ltd., Tokyo, Japan),
and chemical shifts were given on a d (ppm) scale with tetramethylsilane as an internal standard.
Silica gel 60 (Merck, Art. 1.09385; Merck, Darmstadt, Germany), Sephadex LH-20 (Pharmacia
Fine Chemicals, Uppsala, Sweden), Chromatorex ODS (Fuji Silysia Chemical, Ltd., Aichi, Japan)
and Diaion HP20 (Mitsubishi Chemical Industries Co., Ltd., Tokyo, Japan) were used for column
chromatography. HPLC separation was run on a Shimadzu LC-10AS micro pump (Shimadzu Co.,
Kyoto, Japan) with a Shimadzu RID-10A RI-detector (Shimadzu Co., Kyoto, Japan). For HPLC
column chromatography, COSMOSIL 5C18-AR-II (Nacalai Tesque, Inc., Kyoto, Japan, 20mm i.
d. £ 250 mm) was used.
3.2. Plant material
The fruits of L. esculentum ‘Momotarofight’ were collected in August 2008 at the farm of Tokai
University, Kumamoto Prefecture, Japan.
3.3. Extraction and isolation
The smashed ripe fruits of L. esculentum (8998 g) were successively extracted with H2O
(8930 mL) and MeOH (8990 mL) at room temperature. The H2O extract was subjected to Diaion
HP20 (H2O, MeOH, acetone) to yield MeOH-eluted fraction (fr.) (10.3 g) and acetone-eluted fr.
(0.1 g). The MeOH extract was concentrated under reduced pressure to yield a syrup (26.9 g),
which was subjected to Diaion HP20 (H2O, MeOH and acetone) to yield MeOH-eluted fr. (3.8 g)
and acetone-eluted fr. (0.6 g). Both of the MeOH-eluted fractions (frs.) were combined to yield

Natural Product Research
265
fr. 1, which was chromatographed over Sephadex LH-20 [H2O–MeOH (90% MeOH, 100%
MeOH)] to yield frs. 2–4. Chromatography of fr. 2 (5.8 g) over silica gel [CHCl3–MeOH–H2O
(14:2:0.1, 10:2:0.1, 8:2:0.2, 7:3:0.5, 6:4:1, 0:1:0)] furnished frs. 2-1–2-4. Fraction 2-2 (97 mg)
was chromatographed over Chromatorex ODS [H2O–MeOH (30% MeOH, 40% MeOH, 50%
MeOH, 60% MeOH, 70% MeOH, 80% MeOH, 90% MeOH, 100% MeOH)] to yield frs. 2-2-1–
2-2-4. Fractions 2-2-2 (14 mg) and 2-2-3 (11 mg) were each subjected to HPLC (30% MeOH) to
afford 5 (6 mg) from fr. 2-2-2 and 2 (4 mg) from fr. 2-2-3. Chromatography of fr. 2-3 (1.4 g) over
Chromatorex ODS [H2O–MeOH (20% MeOH, 30% MeOH, 40% MeOH, 50% MeOH, 60%
MeOH, 70% MeOH, 80% MeOH, 90% MeOH, 100% MeOH)] furnished frs. 2-3-1–2-3-8.
Fractions 2-3-2 (17 mg), 2-3-4 (120 mg), 2-3-5 (34 mg) and 2-3-7 (18 mg) were each subjected to
HPLC (fr. 2-3-2, 15% MeOH; frs. 2-3-4, 2-3-5, and 2-3-7, 65% MeOH) to yield 1 (7 mg) from fr.
2.3.2, 9 (10 mg) from fr. 2-3-4, 8 (3 mg) from fr. 2-3-5 and 7 (6 mg) from fr. 2-3-7. Fraction 3
(3.7 g) was chromatographed over silica gel [CHCl3–MeOH–H2O (10:2:0.1, 8:2:0.2, 7:3:0.5,
6:4:1, 0:1:0)] to yield frs. 3-1–3-7. Fraction 3-2 (253 mg) was subjected to Chromatorex ODS
[H2O–MeOH (10% MeOH, 20% MeOH, 30% MeOH, 40% MeOH, 50% MeOH, 60% MeOH,
70% MeOH, 80% MeOH, 100% MeOH)] to yield frs. 3-2-1–3-2-4. Fractions 3-4 (102 mg), 3-6
(143 mg), 3-2-2 (29 mg) and 3-2-3 (30 mg) were each subjected to HPLC (frs. 3-4 and 3-6, 30%
MeOH; frs. 3-2-2 and 3-2-3, 20% MeOH) to afford 4 (7 mg) from fr. 3-4, 3 (21 mg) from fr. 3-6,
5 (6 mg) from fr. 3-2-2 and 6 (18 mg) from fr. 3-2-3.
1
25
1: Amorphous powder. ½aꢀD –42.68 (c ¼ 0.8, MeOH). H NMR (pyridine-d5, 500 MHz) d:
5.15 (1H, d, J ¼ 7.5 Hz, Glc0-1), 4.87 (1H, dd, J ¼ 1.5 and 11.5 Hz, Glc-6a), 4.76 (1H, d,
J ¼ 8.0 Hz, Glc-1), 4.54 (1H, dd, J ¼ 1.5 and 12.0 Hz, Glc0-6a), 4.39 (1H, dd, J ¼ 4.5 and
12.0 Hz, Glc0-6b), 4.36 (1H, dd, J ¼ 6.5 and 11.5 Hz, Glc-6b), 4.27* (Glc0-4), 4.26* (Glc0-3),
4.21 (1H, dd, J ¼ 8.5 and 8.5 Hz, Glc-3), 4.16 (1H, dd, J ¼ 8.5 and 8.5 Hz, Glc-4), 4.11 (1H, m,
Glc-5), 4.08* (Agl-1a), 4.06* (Glc0-2), 4.00 (1H, dd, J ¼ 8.0 and 8.5 Hz, Glc-2), 3.99 (1H, dd,
J ¼ 6.5 and 9.5 Hz, Agl-1b), 3.95 (1H, m, Glc0-5), 1.72 (1H, m, Agl-2), 1.51 (1H, m, Agl-3a),
1.11 (1H, m, Agl-3b), 0.94 (3H, d, J ¼ 7.0 Hz, Agl-5), 0.80 (3H, t, J ¼ 7.5 Hz, Agl-4). Asterisk
13
(*) indicates overlapping signals. C NMR (pyridine-d5, 125 MHz) d: 105.5 (Glc0-1), 104.9
(Glc-1), 78.5 (Glc-3), 78.5 (Glc0-3), 78.5 (Glc0-5), 77.3 (Glc-5), 75.3 (Glc0-2), 75.1 (Glc-2), 75.0
(Agl-1), 71.8 (Glc-4), 71.7 (Glc0-4), 70.2 (Glc-6), 62.8 (Glc0-6), 35.4 (Agl-2), 26.4 (Agl-3), 16.8
(Agl-5), 11.4 (Agl-4). Positive FAB-MS m/z: 435 [M þ Na]þ. HR-positive FAB-MS m/z:
435.1836 (calcd for C17H32O11Na: 435.1843).
1
25
8: Amorphouspowder. ½aꢀD –29.38(c ¼ 0.4,MeOH). HNMR(pyridine-d5, 500 MHz)d: 5.54
[1H, d, J ¼ 7.5 Hz, terminal glucosyl group (Glc0)-1], 5.19 [1H, d, J ¼ 7.5 Hz, xylosyl group (Xyl)-
1], 5.15 [1H, J ¼ 8.0 Hz, inner glucosyl group (Glc)-1], 4.99 [1H, ddd, J ¼ 4.5, 7.5 and 7.5 Hz,
aglycone moiety (Agl)-16], 4.90 [1H, d, J ¼ 8.0 Hz, galactosyl group (Gal)], 4.64 (1H, dd, J ¼ 8.5
and 11.0Hz, Gal-6a), 4.61 (1H, d, J ¼ 3.5 Hz, Gal-4), 4.52 (1H, dd, J ¼ 1.5 and 10.5Hz, Glc0-6a),
4.49 (1H, dd, J ¼ 1.5 and 10.0Hz, Glc-6a), 4.41 (1H, dd, J ¼ 7.5 and 9.5 Hz, Gal-2), 4.37* (Glc0-
6b), 4.34 (1H, dd, J ¼ 8.0 and 8.5 Hz, Glc-2), 4.23* (Gal-6b), 4.23* (Xyl-5a), 4.18* (Gal-3), 4.18*
(Xyl-3), 4.17* (Glc0-4), 4.12* (Xyl-4), 4.11 (1H, dd, J ¼ 8.5 and 8.5 Hz, Glc-3), 4.09* (Glc0-3), 4.07
(1H, dd, J ¼ 7.5 and 8.5 Hz, Glc0-2), 4.05* (Gal-5), 4.03* (Glc-6b), 3.95(1H, ddJ ¼ 8.0 and 8.5 Hz,
Xyl-2), 3.94* (Agl-3), 3.93* (Glc0-5), 3.85* (Glc-5), 3.78 (1H, dd, J ¼ 8.5 and 8.5 Hz, Glc-4), 3.68
(1H, dd, J ¼ 10.5 and 10.5Hz, Xyl-5b), 2.70 (1H, q, 7.5), 2.17 (1H, ddd, J ¼ 6.5, 7.5 and 14.0Hz,
Agl-15a), 2.06 (1H, m, Agl-2a), 1.84 (1H, br d, J ¼ 7.5 Hz, Agl-17), 1.81* (Agl-4a), 1.65* (Agl-
12a), 1.61* (Agl-2b), 1.50* (Agl-7a), 1.48* (Agl-1a), 1.40* (Agl-4b), 1.39* (Agl-15b), 1.37* (Agl-
11a), 1.31 (3H, d, J ¼ 7.5 Hz, Agl-21), 1.27* (Agl-8), 1.14* (Agl-6a), 1.11* (Agl-11b), 1.09* (Agl-
6b),1.00(1H,m, Agl-12b),0.92*(Agl-14), 0.90*(Agl-5), 0.81*(Agl-7b), 0.79*(Agl-1b), 0.70(3H,
s, Agl-18), 0.62(3H, s,Agl-19), 0.51(1H,ddd,J ¼ 2.5,8.5and8.5 Hz, Agl-9). Asterisk(*)indicates
overlappingsignals.13CNMR(pyridine-d5, 125MHz)d: 181.1 (Agl-22), 105.1(Glc-1), 104.9(Xyl-
1), 104.8 (Glc0-1), 102.4 (Gal-1), 86.8 (Glc-3), 82.7 (Agl-16), 81.3 (Glc-2), 79.9 (Gal-4), 78.7 (Agl-

266
M. Ono et al.
3), 78.6 (Xyl-3), 77.8 (Glc0-5), 77.6 (Glc0-3), 77.3 (Glc-5), 76.2 (Glc0-2), 75.6 (Gal-5), 75.4 (Gal-3),
75.1 (Xyl-2), 73.2 (Gal-2), 71.1 (Glc0-4), 70.7 (Xyl-4), 70.5 (Glc-4), 67.3 (Xyl-5), 63.0 (Glc-6), 62.5
(Glc0-6), 60.6 (Gal-6), 59.0 (Agl-17), 54.5 (Agl-9), 54.5 (Agl-14), 44.6 (Agl-5), 41.8 (Agl-13), 38.2
(Agl-12), 37.2 (Agl-1), 36.3 (Agl-20), 35.8 (Agl-10), 34.9 (Agl-8), 34.8 (Agl-4), 33.2 (Agl-15), 32.3
(Agl-7), 29.8 (Agl-2), 28.8 (Agl-6), 20.7 (Agl-11), 17.9 (Agl-21), 13.8 (Agl-18), 12.2 (Agl-19).
3.4. Acidic hydrolysis of 1
Compound 1 (1 mg) was heated in 2 M HCl–dioxane (2:1, 1.5 mL) at a temperature of 958C for
1 h. The reaction mixture was extracted with ethyl acetate. The aqueous layer was neutralised
with Amberlite MB-3 (Organo Co., Tokyo, Japan) and then evaporated under reduced pressure
to yield a monosaccharide fr. This fr. was analysed by HPLC under the following conditions:
column, Shodex RS-Pac DC-613 (Showa Denko, Tokyo, Japan, 6.0 mm i.d. £ 150 mm); solvent,
CH3CN–H2O (3:1); flow rate, 1.0 mL/min; column temperature, 708C; detector, JASCO OR-
2090 plus (Jasco, Tokyo, Japan); pump, JASCO PU-2080 (Jasco; and column oven, JASCO CO-
2060 (Jasco). The retention time (tR) and optical activity of the monosaccharide from 1 were
identical with those [tR (min) 6.9; optical activity, positive] of D-glucose.
3.5. DPPH radical-scavenging assay
The DPPH radical-scavenging effect of sample was measured based on the following method
(Blois 1958). The standard assay mixture, in a final volume of 200 mL, contained 10 mL of
sample, 90 mL of 70% ethanol, 100 mL of 0.1 M sodium acetate buffer (pH 5.5). The reaction
was started by the addition of 50 mL of 0.5 mM DPPH freshly prepared in ethanol, allowed to
proceed for 30 min at room temperature. The absorbance of the resulting solution was measured
at 517 nm using microplate reader (SH-1000Lab, Corona Electric, Ibaragi, Japan). Trolox was
used as a positive control. Results presented are the means of four experiments. The DPPH
radical-scavenging effect as percentage of breaching rate of DPPH was calculated by the
following formula:.
ꢀ
ꢁ
Asample 2 Ablank
Acontrol 2 Ablank
DPPHradical-scavenging effectð%Þ ¼ 1 2
£ 100;
where Asample is the absorbance of the sample and Ablank is the absorbance in the presence of
neither any samples nor DPPH solution. Acontrol is the absorbance in the absence of the sample.
4. Conclusion
In this study, we isolated and elucidated the structures of nine compounds from the ripe tomatoes
‘Momotarofight’. Among them, one compound was a new hemiterpene glycoside. In addition,
three aromatic compounds demonstrated DPPH radical-scavenging activities. We previously
isolated and determined the chemical constituents from several other tomato cultivars
(‘Momotaro’, ‘Italian San Marzano’, ‘Chika’ and ‘Komomo’). Therefore, screening for those
compounds in various biological assays may facilitate the delineation of chemically active
constituents from this tomato cultivar. This is a part of our overall goal to fully elucidate the
health benefits of tomatoes. Further investigations are warranted to achieve this goal.
Supplementary material
Supplementary material relating to this article is available online, alongside Tables S1 and S2,
Figures S1–S14.

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267
Acknowledgements
We express our appreciation to Mr. K. Takeda and Mr. T. Iriguchi of Kumamoto University for their
measurement of the MS and NMR spectra.
Funding
This research was supported in part by a Grant-in-Aid for Scientific Research (C) (JSPS KAKENHI [grant
numbers 19590030], [grant number 24590022]) from the Japan Society for the Promotion of Science.
A part of this work was also supported by the Research and Study Project of Tokai University Educational
System General Research Organisation (Kanagawa, Japan).
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