Journal of Agricultural and Food Chemistry
Article
r0 = k[radical][antioxidant]
(5)
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carbazole−coumarin fused two-photon platform: Development of a
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The rate constants (k) of coumarin-fused coumarins together
with Trolox are outlined in Scheme 3. It can be found that k of
+
•
3
(
(only one hydroxyl group contained) in reducing ABTS
(7) Tasior, M.; Poronik, Y. M.; Vakuliuk, O.; Sadowski, B.;
Karczewski, M.; Gryko, D. T. V-Shaped bis-coumarins: Synthesis
and optical properties. J. Org. Chem. 2014, 79, 8723−8732.
−1. −1
−1. −1
0.80 mM s ) is only 0.80 mM s , while those of 4 (two
hydroxyl groups contained) and 6 (three hydroxyl groups
−1. −1
−1. −1
(8) Pardo-Jimen
Encina, P. A.; Olea-Azar, C.; Nun
Synthesis and electrochemical oxidation of hybrid compounds:
́
ez, V.; Barrientos, C.; Per
́
ez-Cruz, K.; Navarrete-
contained) are 8.49 mM s and 41.92 mM s , respectively.
So, the ability of coumarin-fused coumarin to trap radical is
related to the amount of hydroxyl group. The high k values of
̃
ez-Vergara, L. J.; Squella, J. A.
Dihydropyridine-fused coumarins. Electrochim. Acta 2014, 125, 457−
−
1. −1
3
, 4, and 6 in trapping DPPH (0.63, 10.78, and 12.99 mM s ,
4
64.
respectively) and galvinoxyl radical (0.09, 1.37, and 4.36
(
9) Xi, G.-L.; Liu, Z.-Q. Coumestan inhibits radical-induced oxidation
of DNA: Is hydroxyl a necessary functional group? J. Agric. Food Chem.
014, 62, 5636−5642.
−1. −1
mM s , respectively) indicate that coumarin-fused coumarin
prefers to donating the hydrogen atom in −OH to N- and O-
centered radicals. In particular, three hydroxyl groups in 6
increase the radical-scavenging property even higher than that
of Trolox. But k values of 4 (in trapping three radicals) are
higher than those of 5, implying that two hydroxyl groups
locate at the different benzene rings are not beneficial for
scavenging radicals. Moreover, 1 (without hydroxyl group
2
(10) Kim, Y.; Moon, Y.; Kang, D.; Hong, S. Synthesis of heterocyclic-
fused benzopyrans via the Pd(II)-catalyzed C-H alkenylation/C-O
cyclization of flavones and coumarins. Org. Biomol. Chem. 2014, 12,
3413−3422.
(
11) Veselinovic,
́ ́
J. B.; Veselinovic, A. M.; Vitnik, Z. J.; Vitnik, V. D.;
Nikolic, G. M. Antioxidant properties of selected 4-phenyl
hydroxycoumarins: Integrated in vitro and computational studies.
́
+
•
contained) can reduce ABTS , indicating that −N(CH )
makes the scaffold of coumarin-fused coumarin a radical-
scavenger.
3
2
Chem.-Biol. Interact. 2014, 214, 49−56.
(12) Tanemossu, S. A. F.; Franke, K.; Arnold, N.; Schmidt, J.; Wabo,
H. K.; Tane, P.; Wessjohann, L. A. Rare biscoumarin derivatives and
In conclusion, −N(CH ) and the hydroxyl group play
3
2
flavonoids from Hypericum riparium. Phytochemistry 2014, 105, 171−
synergistically antioxidative role for coumarin-fused coumarin
even though they do not locate at the same benzene ring. In
1
77.
(13) Chen, J.; Liu, W.; Zhou, B.; Niu, G.; Zhang, H.; Wu, J.; Wang,
particular, −N(CH ) -involved coumarin-fused coumarin
3
2
Y.; Ju, W.; Wang, P. Coumarin- and rhodamine-fused deep red
fluorescent dyes: Synthesis, photophysical properties, and bioimaging
in vitro. J. Org. Chem. 2013, 78, 6121−6130.
(14) Su, H.; Gornitsky, M.; Velly, A. M.; Yu, H.; Benarroch, M.;
Schipper, H. M. Salivary DNA, lipid, and protein oxidation in
nonsmokers with periodontal disease. Free Radical Biol. Med. 2009, 46,
•
shows the highest activity in inhibiting OH-induced oxidation
of DNA even in the absence of a hydroxyl group. Therefore,
−
N(CH3)2 is an assisting group for the antioxidant
effectiveness in the coumarin-fused heterocycles.
9
(
14−921.
ASSOCIATED CONTENT
Supporting Information
NMR spectra of the synthetic compounds, the decay of the
concentration of radicals together with the calculation of the
■
15) Miura, T.; Fujioka, S.; Iwasaki, H.; Ozeki, M.; Kojima, N.;
*
S
Yamashita, M. Skeleton transformation of α-pyrone induced by 5-aryl
substituent into ring-fused dihydrofuran. Tetrahedron Lett. 2014, 55,
1
536−1539.
(
16) Karthik, G.; Rajasekaran, T.; Sridhar, B.; Reddy, B. V. S. Highly
regio- and diastereoselective three-component reaction of acyclic/
cyclic donor-acceptor carbenoids for the synthesis of angularly fused
furocoumarins and spirooxindolylfurocoumarins. Tetrahedron 2014,
7
(
AUTHOR INFORMATION
■
*
0, 8148−8154.
17) Jang, H.-L.; El-Gamal, M. I.; Choi, H.-E.; Choi, H.-Y.; Lee, K.-
T.; Oh, C.-H. Synthesis of tricyclic fused coumarin sulfonates and their
inhibitory effects on LPS-induced nitric oxide and PGE productions
Notes
2
The authors declare no competing financial interest.
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5
75.
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