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Food Sci. Tec'hno!. Res.

, 10 (2), 152-156, 2004

DPPH Radical-Scavenging Activity and Poly phenol Content in Dried Fruits


MATOBA I '2* K. ISHIWATA,1 T. YAMAGUCHl,2 H. TAKAMURA2,3 and T.
IGraduate School of Human Culture, 2Department of Food Science and Nutrition, and 3KYOUSEI Science Cente/~for
Women's Unive,'.,ity. Kitauoya-Nishimachi, Na,1a, 630-8506 .lapan

Lrf~ and Nature, Nara

Received August 26, 2003; Accepted January 20, 2004

The 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical-scavenging activity and polyphenol content of 25 dried


fruits were evaluated and compared with fresh fruits. The contribution of ascorbic acid to this activity was also

determined. All dried fruits contained DPPH radical-scavenging activity with hawthorn, apricot and blueberry
having the highest. Other dried fruits containing rind also had high activity. The DPPH radical-scavenging activity
and polyphenol content of dried fruits were highly correlated.

Keywords: dried fruits, fresh fruits, ascorbic acid, polyphenol, radical-scavenging activity

Recently it has become evident that free radicals and reactive

Reagents DPPH, L-ascorbic acid, tris(hydroxyrnethyl)aminomethane (Tris), 2,4-dinitrophenylhydrazine, acetoni-

oxygen species injure DNA and biological membrane, and consequently induce cancers, aging and life-style related diseases.

Free radical-scavenging activities are detected in various kinds


of foods (Arai et a/., 200 1 ; Wang and Lin, 2000; Hirota et a/.,

trile (HPLC grade) and Folin-Ciocalteu reagent solution were obtained from Nacalai Tesque Inc. (Kyoto). Ethanol and meth-

anol (HPLC grade) were obtained from Wako Pure Chemical


Industries (Osaka). The water used in this experiment was puri-

2000) and the results of clinical applications have been reported


(Hibatallah et al., 1 999). In addition, the changes of free radi-

fied with Milli-Q Labo equipment (Millipore Japan, Tokyo).

cal-scavenging ingredients during processing and cooking of vegetables have also become evident (Crozier et a/., 1997;
Yamaguchi et a/., 200 1). Therefore, it is anticipated that intake

P/'eparation of mate/'ials Dried fruits from the market were cut into small pieces, smashed in liquid nitrogen and
freeze-dried (Vinson et al., 1998). We used those freeze-dried
fruit powders throughout this work.

of these radical-scavenging ingredients in the daily diet can


prevent cancers, aging and lif~e-style related diseases.

Processed foods, and alcoholic and non-alcoholic beverages with added functional ingredients have been increasing on the

market, and the production and consumption of these functional foods and beverages are also increasing (Chandan,
1999). There are many reports of the functional ingredients in

Measurement of DPPH /'adica/-scavenging ac'tivities Dried fruit powder was first extracted twice by ethanol, and then the residue was extracted twice by water. Before determination, extracts were filtered through a Cosmonice filter-W

(0.45 um, 25 mm i.d.). Measurement of DPPH radical-scav-

enging activities was carried out using the DPPH-HPLC


method (Yamaguchi et a/., 1998). The HPLC analysis was car-

vegetables and fruits. We previously reported the functional ingredients of alcoholic and non-alcoholic beverages (Ishiwata
et a/., 2000, 200la, b).

ried out on a TSK gel Octyl-80Ts column (4.6Xl50 mm,


Tosoh, Tokyo) equipped with a Hitachi L-7420 UV-VIS detector at room temperature. The mobile phase was methanol/water
(70 : 30, v/v) and the flow rate was I ml/min. Detection wave-

Since fresh fruits are rich in radical-scavenging compounds,


dried fruits are also expected to be good sources of these com-

pounds. However, these compounds may be decomposed durIng drying. Therefore, radical-scavenging compounds in dried fruits have to be determined in order to determine the food
function of these fruits.

length was 5 17 nm.

The radical-scavenging activities of ethanol and water extracts were determined separately and summation of the
activities in the two extracts was used. A blank was run without

In this paper, we evaluated I , 1-diphenyl-2-picrylhydrazyl

sample, and Trolox was used as the positive control. Radicalscavenging activity was expressed as ascorbic acid equivalent.

(DPPH) radical-scavenging activity of various dried fruits as

well as ascorbic acid and polyphenol contents, and compared


them to those of fresh fruits.

Measu/~ement ofascol~bic acid Dried fruits were extract-

Materials and Methods


Mate/'ials Dried fruits were purchased from local markets in Nara and Yokohama, Japan. Water content of each dried
fruit was determined by drying method at 1 10'C.

ed by 5% metaphosphoric acid with or without I % stannous chloride to deteamine [dehydroascorbic acid+diketogulonic acid] or Lascorbic acid+dehydroascorbic acid+diketogulonic acidj, respectively. Ascorbic acid was measured by HPLC
according to Kishida et a/. ( 1992). HPLC analysis was carried

out on a Cosmosil C 1 8-AR-II column (4.6x250 nm. Nacalai Tesque) with a Hitachi L-7420 UV-VIS detector at room temperature. The mobile phase was acetonitrile/water (50 : 50, v/v)

*TO whom correspondence should be addressed.


E-mail : matoba@ cc.nara-wu.ac.jp

adjusted at pH 3.5 with 0.1% triethylamine and phosphoric

Radical-Scavenging Activlty in Dried Fruits

153

Table 1. Radical scavengmg actrvlty of dned and fresh frurts


Fruit

Status

Country

Radical-scavenging activity (mg ASA eq/1 OO g dry weight)


875 t 28' >

AsA<'] contribution (o/c) Water content (olo)


O. 1

Apple
Apricot
B anana
B Iueberry

D-rf
F - r!)

China
Japan

4,754i69
3_ ,846lt96
29,4 1 3 It 1 72

O. l

34 84
19

D+rt' F+rf)

China
Japan
PH,*)

D-r
F-r

295 It 1 8

D+r
p+r

PH USA USA
China

547t20
2,869t49
l 6,724 t 80
l ,OIOi3_ 3
6,_529 i 3_ _3

0.0 O.O 0,0 0.0 0.0


l .8

88
lO

77 32 87
3_O

Cherry
Cranberry Fig

D+r
F+r

O.7
O. 1
O. l

D+r D+r
F+r

USA USA
Turkey Japan

78
31 21

3_ ,079 It 22

1,087lt I l

O. 1
O. l O, l

Grape

D+r
F+r

USA
Japan

2,524lt_37 l ,346 t25

79
14

2,883_ i27

O. l

79
31
_30

Hawthom
Ju jube

Kiwlfruit

D+r D+r D-r


F-r

China China China


NZ") Japan Thailand

5,439t68
2,649 t 1 9

2~57t7
2,049 t 3_ 4

0.2 0.0 0.3


3.-5

25 84

Kumquat

Mango
Melon
Muscat
Papaya
Pe ac h

D+r D-r
F-r

1 89t 16
456 It 24
6,84 1 It92

0,0
l .6 1 .2

22
_31

PH
China Japan China
J apan

84

D-r
F-r

440~t 14
2, 1 95 t 83

0.9
2,~3
O. 1

20
87
19

D-r
P-r

l,106i6
l ,374t 1 2
32~5 t 6

O, l
1 .3

Dr F-r
D=r
F-r

PH PH
China
Japan

79 27
87

950t4_3
l ,442t 1 6
l ,949 t 88
1,3_ Ol t6

5.2
O, 1

39
91
~34

0,7
O. l

Pear
Pineapple

D-r
F-r

D-r

Prune

Fr

China Japan Taiwan Taiwan

l ,748 t 66

321 i3

0.3 0.3
1.l

89
*33

798i38
3, 1 12t85
1 0,90 1 i 94

D+r
F+r

USA USA
China China

Rakanka
Strawberry

D+r D-r

3 ,213_ i 123

0.0 0.0 0.0


O. l

79 40 79
9

l ,997 i 62

26

")ASA contribution, ascorbic acid content/radical-scavenging activity>< 100% b)D-r, Dried fruits without rind. ' ) Data were meanstSD of three
determlnauons. '!) F-r, fresh fruits without rind. ") D+r, dried fruits with rind. f) F+r, fresh fruits with rind. ,~) pH, Philippines. h) NZ. New Zealand.

acid at the flow rate of I ml/min. Detection wavelength was at

ever, dried fruits generally contained higher activity than fresh

505 nm. Ascorbic acid content was calculated by subtraction of [dehydroascorbic acid+diketogulonic acidl from [ascorbic
acid + dehydroascorbic acid + diketogulonic acidj .

fruits. These results suggest that the dried fruits, especially


those with rind, are a good source of radical-scavenging activity.

Measurement (if Po!yphenol c'ontent Dried fruits were extracted by 80% methanol. Measurement of polyphenol content was carried out according to Singleton and Rossi ( 1965)
and Kahkonen et a/. ( 1999) using Folin-Ciocalteu reagent solution .

Radic'a/-scavenging activity in /~ind and pulp of .files/7

f,uits Since high and pulp of fresh fruits radical-scavenging activ dried fruits with rind, the activity in rind
was determined (Table 2). In all fruits except apricot, the activ-

ity of rind was higher than that of pulp. However, fresh fruits
are usually eaten without the rind. Therefore, dried fruits with
rind are suitable for efficient intake of radical-scavenging activity.

Results and Discussion


Radica/-scavenging activities oj' d/'ied and fresh f7-uits

DPPH radical-scavenging activity of 22 kinds of dried fruits


and 1 6 kinds of fresh fruits corresponding to the dried fruits are

Leong & Shui (2002) reported that the contribution of ascorbic acid to radical-scavenging activity in fresh fruits was higher

shown in Table I . Among dried fruits, hawthorn contained the


highest radical-scavenging activity. Dried fruits with rind such

than our results. This may be due to the difference in the meth-

as apricot, cranberry, prune, and rakanka also contained high


activity. However, the contribution of ascorbic acid was negligi-

ods used, as previously reported by Murakami et a[, (2002). They determined 2,2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radical-scavenging activity, while we used
DPPH radical . Polyphenol c'ontent o,f d/-ied and,fresh fr'uits Polyphenol

ble in dried fruits, which suggests that the radical-scavenging

activity may originate from other active compounds such as polyphenols. Table I also shows that the radical-scavenging
activity of dried fruits was lower than that of the corresponding fresh fruits on a dry weight basis. On a fresh weight basis, how-

content of dried and fresh fruits is shown in Table 3. Among dried fruits, hawthorn contained the largest amount of total
polyphenols, followed by blueberry, grape, and apricot. In addi-

l 54

K. IsHIWATA et a/.

Table 2. Radical scavengmg actrvrty of pulp and nnd of fresh frults


Pruit

Country
J ap an

Part

Radical-scavenging activity

(mg ASA eq/lOO g dry weight)


l 7,0 1 O t 84"'

AsA") contribution (olc)


O. 1
O, l O, 1

Water content (olc)

Apple
Apricot
B anana

rind

71

Japan
J apan

pulp

4,75~5 t 69

rmd
pulp

9,006t68
20,_5 1 6i I _35

Japan PH'

O,O
O, l

84 87 88

nnd
pulp
rind

l ,099i I l

70
77 75

PH
Fig

547 It 20
3_ ,420t I OO

O, l
O. 1

Grape
Kiwifruit

Japan Japan Japan


J apan

pulp
rind

2,524i37
l I , 1 26t42

O, 1

79
77
81

0,0
O. 1

pulp
rind

1,283 t57
16,459t 13_ 4

NZ'~

0,2
3,.5

65

NZ
Mango
Muscat
Papaya
Peach
Pe ar

pulp

2,049 t 34

PH PH

nnd
pulp
rind

24,802t78
6,84 1 i92

0,0 0,6
O, l

84 75 80
81

Japan Japan

3,458i80
1 ,374 It 62

pulp
rind

O, 1

PH PH
J ap an

4,0_56i77

pulp
rind

950t42
8 ,460 t 67
1 ,949 It 88

0,7 5,2
O, l

82
87

76
91

Japan Japan
J ap an

pulp

nnd
pulp

2,4 16lt 17
l ,748 It 66

Prune

USA USA

nnd
pulp
content/radical-scavenging

4,906 t 80
l ,375 i 6

0.7 0,2 0.3 O,O


O, l

74 79 70
84
' ) PH,

") ASA contribution, ascorbic acid p]nes. '!' NZ, New Zealand.

actrvrty X I OO%, h) Data

were meanstSD of three determinations.

Philip-

Table 3. Polyphenol content of dried and fresh fruits.


Fruit

Status
D-rl')
F-f !)

Country

Total polyphenols

(mg GAE"yIOO g dry weight)


916lt7')

Aglycons (mg GAE/lOO g dry weight)


103t 1 470 t 28
63_ 4lt 1 2

(%)
l I .3

Apple
Apricot

China
Japan

2,168t38
2,256i 1 3 3 ,062lt25

2 1 .7

D + r'
F - rf)

China
J ap an

28, 1

2,3 30t52
25 It O

76. l
6. 1

Banana
Blueberry

Dr F-r
D+r
F+r

PH,*>

413t3
804 t 5
2,83_ 2lt4

PH

244 t 3

30.3
6.-5

USA USA
China

185i2
2,390t 1 4

3_ ,590t3 l

66.6
27 , ~3

Cherry
Cranberry Pig

D+r
F+r

828lt7
l ,O17t28

226i 14
265 i 5 l

D+r D+r
F+r

USA USA
Turkey Japan

26. l

1,819t8
l ,234i4 1
l ,699 t 24

3 32t6
136t 1 6

18.2
l 1.0

361 t3
3_54lt5

21.3
14.7

Grape

D+r
F+r

USA
Japan China

2,414+7
3,202lt_50 3,563+ 1 1

939t I l

29.3
3 1 .9

Hawthorn
J u jube

Kiwifruit

D+r D+r D-r


F-r

l,13_8t5

China China
NZ" '

1,152+4

3 50t4

758+6
930+ 1 1

276+4
676+ I _5

Kumquat

Mango
Melon
Muscat
Papaya

D+r D-r
F-r

Japan Thailand

530+4 885+9
1 ,448 + 9 l

193+5
323 + 6 544 + 24

30,4 36.4 72,7 36.5


36,-5

PH
China
Japan

D-r
F-r

55_5+8
l ,042 t 1 7

l +0

37,6 O.2
13,2 14.0 19,5

13_8+2
163 + 10 304 + 2 284 t 3

D-r
F-r

China
Japan

l,161+43
l ,558 i24

D-r
F-r

PH PH
China
J apan

389+2 510+8
l ,260 t 29
1,83_ 3 + 13

236i2
222 t 1 6
3_ 98lt2

73.0 46.3
17.6 21.7 26.4
24, l

Peach
Pear Pineapple

D-r
F-r

D-r
F-r

China
Japan

l,196i21
l ,328t 1 4

316t7
321 i6
293 i 3

D-r
F-r

Taiwan Taiwan

802i5
1 ,248 t 1 3

36,5

349+ I O

27.9
17.7

Prune

D+r
F+r

USA USA
China China

l ,O_32i6

183+3
509 + 5

1350i7
2,007 + 20
l ,162lt 17

37.7
~34.7
3~ 2,8

Rakanka
Strawberry

D+r D-r

697+ 1 3

382i6
d)F-r, fresh fruits without rind.

") GAE, gallic acid equivalent. !'i D-r, dried fruits without rind. fruits with rind. r,F+r, fresh fruits with rind. ,*) PH. Philippines

< ) Data were meanstSD of three determinations. ") NZ, New Zealand.

<') D+r, Dried

Radical-Scavenging Activity in Dried Fruits

l_55

4000
Rs0.831

Hawthern
,::

~ 3000
~,

o B~ueberry
e ra ~e

O a) o o -J U < 2000 (:)


o)

o
R~kanka

O Apricot

S
~0$:

O eranbefry

Fig

_>0 1000
CL

~uscat~ pear e~eh O Str~wberrV OJujt~be o

eapple o PPie
fru~t

~ange

_~~ xi~ o Kuttx


o

CP O Cherry
enas

Prwe

at o rx~~,F~ek)tl

\v papaya

O 1000
Fig. l.

2000

3000

Radicai~;cavenging Aetivity (mg Ascorbic Acid eq!100g Dry Weight)

4000 SOOO

Correlation betwcen radical-scavenging actlvlty and total polyphenols in dried fruits. GAE, gallic acid equivalent.

Table 4. Polyphenol content of pulp and nnd of fresh frurts


Fruit

Country
J apan

Part

Total polyphenols (mg GAE">/10O g dry weight)


3,_555 t 35/"

Aglycons
(mg GAE/1 OO g dry weight)
2,_33_ 5 i 27
(clc)

Apple
Apricot
B anana

rind

Japan
J ap an

pulp
rind

2, 168lt3 8

470t28
97 1 i23

1 ,390t 38
3 ,063 t 24
2,799 t 1 3

65.7 21.7 69.9


76. 1

Japan PH'

pulp

rmd
pulp
rind

2,330lt35 l ,724i9
244 It 3

PH
Fig

804 i 5
2,092 i 1 7
1 ,699 t 24
l ,450 jl 24

Japan Japan
J ap an

798lt6
361 It3

pulp
rind

Grape
Kiwifruit

Japan
NZ'!'

pulp

442t~3
l ,282 It 24

I ,280t 14 74 t 6
l ,068~t 10

61.6 3O.3 3X.2 21.3 88.3


l 6.7

nnd
pulp
rind

NZ
Mango
Muscat
Papaya
Peach
Pear

930lt I l
l 6.47_5 It 1 89

676t I _5

PH PH

14, 157t 1 27
544 It 24

pulp

l ,448 t 9 1

Japan
J ap an

nnd
pulp

3 .418t52
l ,5_58 It 24

2,061 i 12 304 i 2

83.3 72.7 85.9 37.6 60.3


19.5
l .6

PH PH
Japan Japan
J ap an

nnd
pulp
rind

744 t 9
51Oi8

12lt3

236t2
l,013 t 15
398 It 2
I ,958 t 8

46.3
44 . 9
2 1 .7

2,2_58i30
l.833_ i 13

pulp
rind

2.013_ jl24
1 ,328 t 1 4

97.3
24. 1
8 1 .O

Japan

pulp

3 21 i6

Prune

USA USA

rmd
pulp

4,6O8 It 55
1 .800 i 38

3,730t20
l ,424 t 33

79. l

"} GAE, Gallic acid equivalent. !') Data were meansiSD of three determinations. ' ) PH.

Philippines.

</] NZ, New Zealand.

tion, the total polyphenol content of dried fruits with rind was

In this study, individual polyphenolic compounds could not


be determined, however, polyphenols in some fresh fruits have
been reported: cyanidin and peonldin-3-galactose in cranberry (Kankdnen et a!., 2001); cyanidin and chlorogenic acid in blue-

high. The fruits containing high DPPH radical-scavenging


activity tended to contain a large amount of polyphenols; as
shown in Fig. I , these two factors are highly correlated in dried

fruits. These results suggest that the contribution of polyphenols to radical-scavenging activity is large in these fruits.

berry (Tsushida, 1 998) and prune (Donovan et a/., 1998); and


catechin, epicatechin, gallic acid and malvidine-3_ -glucoside in

Table 3 also shows that the polyphenol content of dried fruits

grape (Iwashina, 1994). Further study on individual compounds in fresh and dried fruits is necessary.

was lower than that of the corresponding fresh fruits on dry

weight basis. The ratio of aglycons was also lower in dried fruits. Aglycons probably became more decomposed than glycosides during preparation of the dried fruits, since aglycons are less stable than glycosides (Rice-Evans & Miller, 1 996;
Chuda et a/., 1998).

Polyphenol content of rind and pulp of fresh fruits was deter-

Po!ypheno/ content oj' rind and pulp of ,

mined (Table 4). In all fruits except apricot, the polyphenol


content of rlnd was higher than that of pulp, as true of the radi-

cal-scavenging activity. Since fresh fruits are usually eaten

156
without rind, eating dried fruits with rind are a good means of
493.

K. ISHTWATA et a!.

efh~cient intake of polyphenols as well as radical-scavenging


activity.

Ishiwata, K., Murakami, M., Takamura, H, and Matoba, T. (200la). Changes in the DPPH radical-scavenging activity and ascorbic acid
content of commercial beverages during preservation. J. Cook. Sci.
,lpn., 34, 68-72.

Conclusions Among the dried fruits examined, hawthorn, apricot and


blueberry had the highest radical-scavenging activity. Though
ascorbic acid did not contribute to this activity, polyphenol con-

Ishiwata, K., Takamura, H, and Matoba, T. (200lb). DPPH radical-scavenging activity of commercial alcoholic drinks. ./. Cook. Sci. .lpl7., 34,
407J~ 1 7.

lwashina, T. ( 1 994). Flavonoids of fruits. Food /nd., 37, 52~9.

Kahkdnen, M.P., Hopia, A.1. and Heinonen. M. (2001). Berry phenolics


and their antioxidant activity. ./. Ag,'i('. Food Chen7., 49, 4076~082

tent was highly correlated with it. Since dried fruits, especially

with rind, contain high radical-scavenging activity and


polyphenol content, they as well as fresh fruits are considered
healthy and suitable for preventing life-style related diseases.

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