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Flavonoids and Their Free Radical Reactions: Wolf Bors, Christa Michel, Kurt Stettmaier
Flavonoids and Their Free Radical Reactions: Wolf Bors, Christa Michel, Kurt Stettmaier
Flavonoids and Their Free Radical Reactions: Wolf Bors, Christa Michel, Kurt Stettmaier
Flavonoids
and their free radical reactions
Wolf Bors, Christa Michel, Kurt Stettmaier
Inst. Strahlenbiol., GSF Research Center
D-85764 Neuherberg, Germany
ph.: (+49-89) 3187-2508
fax: (+49-89) 3187-2818
e-mail: bors@gsf.de
Flavonoids
W. Bors et al. 1
Flavonoids - Contents
Introduction
Structure, occurrence and nomenclature
flavonoids in general
flavan-3-ols (catechins)
proanthocyanidins (condensed tannins)
Functions - in vitro
radical scavengers
redox properties
mechanisms of radical interactions
Flavonoids
W. Bors et al. .2
Flavonoids - Introduction
Flavonoids
W. Bors et al. .3
Flavonoids - Introduction
Since the early fifties, their antioxidant potential with regard
(Bors W et al. (1996) in: Handbook on Antioxidants, Cadenas & Packer, eds, Dekker, New York,
pp. 409.)
Flavonoids
W. Bors et al. 4
OH
B
O
Chalcone
O
C
O
OH
OH
Flavanone
Flavan-3-ol
Dihydroflavonol
+
O
OH
OH
Anthocyanidin
Flavon-3-ol
Flavone
Isoflavone
Neoflavone
Flavonoids
W. Bors et al. .5
Procyanidin dimers
Flavan-3-ols
OH
OH
2'
HO
7
6 A
5
3 ' 4'
OH
OH
B 5'
HO
6'
HO
2
4
OH
OH
OH
OH
OH
OH
OH
(+ )-ca te ch in (C AT )
(-)-ep icate ch in (E C )
F
HO
OH
O
HO
OH
O
C
OH
OH
HO
OH
OH
OH
OH
OH
OH
HO
OH
pro cyan id in A 2 (P C -A )
OH
OH
OH
HO
OH
HO
OH
OH
OH
C
OH
OH
O
C
OH
OH
HO
OH
OH
F
OH
OH
OH
OH
OH
p ro cy an idin B 2 (P C -B )
The nomenclature for the flavan-3-ols is rather confusing, as it is based both on the actual
structure, the chemical identification, and derivations thereof. For the proanthocyanidin
oligomers, a highly systematic nomenclature exists, based on the structures of the
monomers and the attachment sites.
(Kaul (1996) Pharmazie uns Zeit. 25:175.)
Flavonoids
W. Bors et al. 6
N3
t-BuO
66
50
1.35
64
51
210
52
2.65
dihydrofisetin (3,7,3,4-tetra-OH)
67
56
eriodictyol (5,7,3,4-tetra-OH)
117
47
0.8
dihydrokaempferol (3,5,7,4-tetra-OH)
dihydroquercetin (3,5,7,3,4-penta-OH)
58
103
89
43
0.95
1.0
45
62
Flavones
apigenin (5,7,4-tri-OH)
135
48
3.0
130
41
5.7
141
51
88
66
6.0
6.6
Flavanols
(+)-catechin (3,5,7,3,4-penta-OH)
(-)-epicatechin ( - - )
Flavanones, Dihydroflavonols
naringenin (5,7,4-tri-OH)
luteolin (5,7,3,4-tetra-OH)
Flavonols (3-hydroxyflavones)
kaempferol (3,5,7,4-tetra-OH)
quercetin (3,5,7,3,4-penta-OH)
Flavonoids
W. Bors et al. 7
k
l
30
20
j
i
10
TEAC
e
d
a
c
b
rel.units
-1 -1
k [10 M s ]
40
3
2
1/IC50(DPPH)
1
0
10
15
10 15 20 25 30
20
25
30
W. Bors et al. 8
Flavanols
300
400
Eriodictyol
Luteolin
Flavones
Dihydro fisetin
Fisetin
Flavonols
Dihydro quercetin
Quercetin
500
600
700
Wavelength
|----| 2G
The transient spectra observed with the pulseradiolytic technique reflect the B ring semiquinones for all compounds with a saturated C
ring (2,3-single bond). Desaturation leads to
expanded delocalization of the odd electron
over the whole three-ring system.
Flavonoids
W. Bors et al. 9
2+
HRP/H2O2+Zn
CAT
HRP/H2O2
EGCG
0
EC
93 s
EGC
ECG
152 s
|-----|
EGCG
5G
TA
|-----| 0
5G
For catechins, the propensity for oligomerization is reflected in the EPR spectra
as well, leading from well-resolved signals
to single line signals of polymers.
(Bors W et al. (2000) Arch Biochem Biophys.
374:347.)
W. Bors et al. 10
[0]
[1]
OH + N3
F lO H
[2]
[3]
[4]
N 3 + F lO
+ A sc
F l= O + A sc
[8]
F lO
+ H
2 F lO
[7a,b]
N3
F lO
[6]
N 3 + A scH
[5a,b]
+ A sc
+ A sc
[9]
F lO
[10]
2 A sc
+ H
F lO
F lO
A sc
3 N2
F lO
F lO H + F l= O
F lO
N3 + OH
+ N3
+ N3
+ A scH
F lO
F l= O + A scH
A scH
+ DHA
+ DHA
rep resent th e tw o un iv alen t redo x eq uilibria, reactio ns [8 ] an d [9 ] are tw o rad ical/rad ical
elim in atio n reaction s, th e direction d eterm in ed b y th e resp ective red u ctio n p oten tials.
|-------| 5G
+ DHA
+ H+
Redox properties
+ H+
W. Bors et al. 11
OH
OH
OH
disprop.
OH
OH
O
O2
reduction
disprop.
O 2O
O
O
OH
OH
Flavonoids
W. Bors et al. 12
O
H
HO
O
OH
O
O
OH
O
O
O
H
HO
O
O
Mechanism of radical
interactions - flavonols
OH
O
OH
O
O
HO
O
O
O
O
OH
OH
O
O
OH
O
OH
Flavonoids
OH
W. Bors et al. 13
O
O
OH
EGCG
OH
O
OH
OH
OH
[O]
OH
O
HO
O
O
O
OH
O
OH
EGCG quinone
OH
OH
+ EGCG
OH
OH
OH
HO
H O
HO
OH H
H
H
HO
H
OH
HO
HO
OH
HO
OH
OH
HO
OH
OH
OH
HO
HO
O OH
OH
OH
H
O
O
OH
OH
OH
O
OH
OH H
H
OH
OH
HO
OH
EGCG dimer
2',4 adduct
NMR sensitive
Flavonoids
EGCG dimer
2',2" gallyl adduct
NMR insensitive
W. Bors et al. 14
Flavonoids
W. Bors et al. 1