Characterization of avonoid 3-Methoxyquercetin performed by FT-IR

and FT-Raman spectroscopies and DFT calculations

T.A. de Toledo
a
, L.E. da Silva
b
, T.C. Botelho
c
, R.J. Ramos
a
, P.T. de Souza Jr.
c
, A.M.R. Teixeira
e
,
P.T.C. Freire
d
, R.R.F. Bento
a,
a
Instituto de Fsica, Universidade Federal de Mato Grosso, Cuiab, MT 78060-900, Brazil
b
Setor Litoral, Universidade Federal do Paran, Matinhos 83260-000, Brazil
c
Departamento de Qumica, Universidade Federal de Mato Grosso, Cuiab, MT 78060-900, Brazil
d
Departamento de Fsica, Universidade Federal do Cear, Fortaleza, CE 60455-760, Brazil
e
Departamento de Fsica, Universidade Regional do Cariri, Crato, CE 63010-970, Brazil
h i g h l i g h t s
" Synthesis of avonoid.
" Physical characterization of a substance.
" Density Functional Theory, Raman and infra red studies.
a r t i c l e i n f o
Article history:
Received 4 May 2012
Received in revised form 27 June 2012
Accepted 27 June 2012
Available online 4 July 2012
Keywords:
3-Methoxyquercetin
Flavonoids
Vibrational spectra
DFT calculations
a b s t r a c t
In the present study, the natural product 3-Methoxyquercetin, a avonoid with potential antiviral activ-
ity, was characterized through infrared and Raman spectroscopies combined with Density Functional
Theory calculation. The avonoid was extracted from Strychnos pseudoquina St. Hil (Loganiaceae) by chro-
matographic techniques. The optimized molecular structure and calculated vibrational spectra were
performed by B3LYP/6-31G (d,p) basis set. The optimized structure was compared with X-ray diffraction
data of other avonoids compounds, and the theoretical data are in good agreement with experimental
ones. Fourier transformRaman and infrared spectra, as well as the assignment of the normal modes are
also presented.
2012 Published by Elsevier B.V.
1. Introduction
Flavonoids are polyphenolic compounds produced by plants,
being important in plant growth and in defense mechanisms [1].
These compounds are commonly found in fruits, vegetables, nuts,
cereals and beverages such as tea and red wine [25]. Flavonoids
are widely distributed in the plant kingdom and ingested daily
by humans [6,7]. Therefore, their use as potential therapeutic com-
pounds against a variety of diseases is of great interest. For centu-
ries, preparations containing avonoids have been used to treat
human diseases and many biological and pharmaceutical proper-
ties have been attributed to this class of compounds. Some avo-
noids possess signicant anti-hepatotoxic [8], anti-HIV-1 [9,10],
antitumor [11], antioxidant [12] and anti-inammatory activities
[1315]. The antioxidant properties of avonoids are often claimed
to be responsible for the protective effects of these compounds
against cardiovascular disease, certain forms of cancer, photosensi-
tivity diseases and inammations [1619]. Flavonoids can also in-
hibit a wide range of enzymes involved in oxidation systems, such
as 5-lipoxygenase, cyclooxygenase, monooxygenase, or xanthine
oxidase [2022].
Many natural and synthetic avonoids are described as having
an antipoliovirus activity [2327]. The avonoid compound
3-methylquercetin, (3-MQ), showed potent activity against poliovi-
rus type 1 proving to be the most promising agent with in vitro
antiviral activity against polio-, coxsackie- and rhinoviruses (at
concentrations as low as 10 ng/mL) [23,28]. At a dose of 20 mg/
kg, the compound 3-MQ protected mice against lethal infection
with coxsackie virus B4 [25]. Moreover, the compound 3-MQ inhib-
its the synthesis of viral RNA, both in infected cells and in cell free
systems [25,2930].
0022-2860/$ - see front matter 2012 Published by Elsevier B.V.
http://dx.doi.org/10.1016/j.molstruc.2012.06.058

Corresponding author. Tel.: +55 65 3615 8743.

E-mail address: ricardobento@sica.ufmt.br (R.R.F. Bento).
Journal of Molecular Structure 1029 (2012) 2227
Contents lists available at SciVerse ScienceDirect
Journal of Molecular Structure
j our nal homepage: www. el sevi er . com/ l ocat e/ mol st r uc
Structureactivity relationship studies have shown that 3-
methoxyl and 5-hydroxyl groups of the avone skeleton are neces-
sary for specic antirhinoviral activity, while 3-methoxyl and
4-hydroxyl groups are responsible for the antipolioviral effect
[27,31].
Recently, Fourier Transformed Infrared (FT-IR) and Fourier
Transformed Raman (FT-Raman) spectroscopy techniques com-
bined with Density Functional Theory (DFT) calculations have
been used as important tools to study molecules and biological
compounds [32,33]. The theoretical calculations could help the
interpretation of the experimental spectra [34]. In addition,
DFT calculations are useful to study electronic structure, calcu-
late energy of molecules and solids with a good accuracy level
[35].
In the present work, we report the characterization of natural
product 3-Methoxyquercetin (3-MQ), C
6
H
12
O
7
, performed by FT-
IR and FT-Raman techniques and DFT calculations. The FT-IR and
FT-Raman spectra of the molecule were recorded at room temper-
ature. In order to assignment the normal modes of the molecule
DFT calculations were performed with B3LYP/6-31G(d) method.
The experimental spectra were compared with the theoretical
ones. Furthermore, the theoretical spectra were analyzed in terms
of the potential energy distribution (PED) using VEDA [36] soft-
ware. We compare our optimized parameters with X-ray diffrac-
tion data of other avonoid compounds reported in literature
[37,38].
2. Experimental
The avonoid was extracted from Strychnos pseudoquina (SPQ)
St. Hil (Loganiaceae) by chromatographic techniques. SPQ is a med-
ium-size tree founded in the Mato Grosso cerrado in Brazil [39].
The FT-IR spectrum was recorded using a Shimadzu Prestige-21
Spectrometer in the region 4000400 cm
1
. A spectral resolution
of 4 cm
1
was used and the spectra were accumulated over 20
scans. The samples were prepared as KBr disk. The FT-Raman spec-
troscopy was record using a Bruker Ram II FT-Raman-Vertex 70 FT-
IR micro-spectrometer equipped with a D418-T detector. Radiation
of 1064 nm line from Nd: YAG was used to excitation. The laser
power was 150 mW. The FT-Raman spectrum was measured in
the region 504000 cm
1
.
3. Computational methods
The Density Functional Theory (DFT) calculations were carried
out using Beckes 3-parameter hybrid combined with the Lee
YoungParr correlation functional (B3LYP) [40,41]. The optimized
structural parameters and vibrational wavenumbers for 3-MQ
were performed with restricted B3LYP with 6-31G (d,p) basis set.
Our calculations were done with a single molecule in gas phase
using the Gaussian 03 software [42]. The optimized structure
was calculated without imaginary frequency, proving that station-
ary point was founded [32,43]. In addition, DFT calculations were
utilized to obtain harmonic force constant, which were then used
to predict the fundamental vibrational wavenumber for compari-
son with the experimental results. The Raman activities calculated
with Gaussian 03 program were converted to relative Raman
intensities using the relationship derived from the intensity theory
of Raman scattering [44,45]. The formula of the theoretical Raman
intensities can also be found in the articles: Wysokin ski et al. [46]
and Michalska et al. [47]. The simulated spectra were plotted using
a pure Lorentzian band shape with a bandwidth (FWHM) of
10 cm
1
.
4. Results and discussions
4.1. Molecular structure
The basic structure of any avonoid compound is characterized
by two aromatic rings (AB) linked by a pyrone ring (C) [48,49]. The
molecular structure and atom numbering scheme of 3-MQ is
shown in Fig. 1. Our optimized bond distance, bond angle and tor-
sion angle calculated by B3LYP/6-31G (d,p) method are listed in
Table 1.
We compare our optimized molecular parameters with the
X-ray diffraction data from similar avonoid compounds reported
Fig. 1. The molecular structure and numbering label of avonoid 3-MQ.
Table 1
Geometric parameters calculated of optimized molecular structure of avonoid 3MQ.
Bond lengths () Bond lengths ()
C1AC2 1.391 O1AC3 1.361
C2AC3 1.397 O1AC4 1.376
C5AC1 1.401 O2AC1 1.361
C6AC5 1.391 O3AC6 1.352
C7AC3 1.404 O4AC8 1.231
C8AC7 1.474 O5AC9 1.367
C8AC9 1.478 O5AC16 1.438
C9AC4 1.366 O6AC12 1.378
C4AC10 1.471 O7AC13 1.359
C10AC15 1.406 C13AC12 1.407
C11AC12 1.384 C14AC13 1.392
C15AC14 1.393
Bond angle () Bond angle ()
C1AC2AC3 118.15 C14AC13AC12 118.95
C2AC3AO1 114.92 C15AC14AC13 120.66
C3AO1AC4 122.13 C16AO5AC9 116.26
C4AC10AC15 122.78 O1AC4AC10 111.22
C5AC1AC2 120.72 O2AC1AC5 116.64
C6AC5AC1 120.29 O3AC6AC5 120.93
C7AC3AO1 121.62 O4AC8AC9 120.93
C8AC7AC6 124.12 O5AC9AC8 118.15
C9AC4AO1 119.9 O6AC12AC13 114.73
C10AC15AC14 120.76 O7AC13AC14 120.51
C11AC12AC13 120.74
Torsion angle () Torsion angle ()
C1AC2AC3AO1 179.64 O1AC4AC10AC11 19.55
C2AC3AO1AC4 178.75 O2AC2AC5AC1 0.06
C3AO1AC4AC10 181.62 O3AC5AC7AC6 0.26
C5AC1AC2AC3 0.13 O4AC7AC9AC8 0.30
C6AC5AC1AC2 0.24 O5AC4AC8AC9 3.44
C10AC15AC14AC13 0.04 O6AC11AC13AC12 0.07
C11AC12AC13AC14 0.12 O7AC12AC14AC13 0.14
C15AC14AC13AC12 0.32 C16AO5AC9AC4 120.90
T.A. de Toledo et al. / Journal of Molecular Structure 1029 (2012) 2227 23
Table 2
Calculated vibrational wavenumbers (in cm
1
) unscaled and scaled by the scale factor 0.9613, experimental Raman band positions in units of cm
1
and assignment of vibrational
modes.
x
cal
x
scaled
x
FT-Raman
x
FTIR
Assignment with PED (%)
26 25 s[O1AC4AC10AC11] (80)
37 36 D(C4AC11AC23AC10) (20); s(C3AO1AC4AC10) (40)
56 54 56 D[C8A3-C6AC7] (11); s[C3AO1AC4AC10] (16); s[C2AC3AO1AC4] (39)
62 60 s[C16AO5AC9AC4] (21)
81 78 78 d[C4AC10AC15] (21); d[O1AC4AC10] (29)
98 94 104 s[C16AO5AC9AC4] (34); s[C5AC1AC2AC3] (12)
136 131 134 D[C7AC2AO1AC3] (13); s[C15AC14AC13AC12] (15); s[C1AC2AC3AO1] (11)
150 144 s[C16AO5AC9AC4] (15); s[HAC16AO5AC9] (12); s[HAC16AO5AC9] (31)
190 183 D[O5AC4AC8AC9] (13); d[C16AO5AC9] (12)
210 202 s[C6AC5AC1AC2] (10); s[HAO6AC12AC11] (22)
215 207 s[C6AC5AC1AC2] (22); s[HAO6AC12AC11] (53)
221 212 s[C6AC5AC1AC2] (11); s[C11AC12AC13AC14] (27); s[HAAO6AC12AC11] (14)
223 214 235 d[C10AC15AC14] (11); d[C2AC3AO1] (10); m[C4AC10] (15)
250 240 243 d[C4AC10AC15] (20)
256 246 272 s[C3AO1AC4AC10] (10); s[C1AC2AC3AO1] (26)
294 283 D[C8AC3AC6AC7] (32); s[C5AC1AC2AC3] (15)
299 287 d[O6AC12AC13] (11); d[O1AC4AC10] (12)
313 301 308 d[O6AC12AC13] (33); d[O7AC13AC14] (41)
333 320 d[O2AC1AC5] (24); d[O3AC6AC5] (19)
352 338 346 D[O7AC12AC14AC13] (19)
358 344 d[O5AC9AC8] (18); d[O4AC8AC9] (37)
374 360 380 s[HAO2AC1AC2] (92)
430 413 418 s[HAO3AC6AC5] (47)
435 418 s[HAO3AC6AC5)] (40)
447 430 443 D[O6AC11AC13AC12] (14); D[O7AC12AC14AC13] (14); s[C10AC15AC14AC13] (10);
s[C15AC14AC13AC12] (16); s[HAO7AC13AC12] (22)
465 447 465 s[HAO7AC13AC12] (72)
476 458 484 d[O7AC13AC14] (17); d[C14AC13AC12] (19)
495 476 519 D[C9AC10AO1AC4] (16); d[C16AO5AC9] (25)
531 510 528 d[O3AC6AC5] (28); d[C1AC2AC3] (12)
561 539 s[C10AC15AC14AC13] (21)
573 551 578 d[C6AC5AC1] (18)
594 571 600 598 d[O6AC12AC13] (21); d[O7AC13AC14] (12)
608 584 d[C15AC14AC13] (19)
617 593 D[O3AC5AC7AC6] (32); s[HAC5AC1AC2] (12)
633 609 D[O2AC2AC5AC1] (17); d[C5AC1AC2] (12)
639 614 640 640 D[O2AC2AC5AC1] (25)
660 634 674 671 D[C4AC11AC15AC10] (12); D[C9AC10AO1AC4] (21); D[O6AC11AC13AC12] (17)
691 664 687 686 D[C7AC2AO1AC3] (13); D[O3AC5AC7AC6] (13)
768 738 721 719 D[C7AC2AO1AC3] (13); D[O5AC4AC8AC9] (10); D[O4AC7AC9AC8] (49); s[HAC2AC1AC5] (12)
782 752 731 755 D[O2AC2AC5AC1] (11); D[O4AC7AC9AC8] (12); s[HAC2AC1AC5] (54)
804 773 796 m[O6AC12] (11); m[O7AC13] (15); m[C13AC12] (36); m[C14AC13] (11)
805 774 809 808 D[O2AC2AC5AC1] (11); s[HAC5AC1AC2] (10)
840 807 835 s[HAC15AC14AC13] (23); s[HAC14AC15AC10] (42); s[HAC11AC12AC13] (15)
849 816 844 840 d[C3AO1AC4] (12); d[C10AC15AC14] (18)
862 829 893 877 s[H(34)AC14AC15AC10] (10); s[HAC11AC12AC13] (57)
924 888 915 912 d[C5AC1AC2] (10); d[O4AC8AC9] (13); m[O5AC9] (11)
962 925 973 971 s[HAC15AC14AC13] (53); s[HAC14AC15AC10] (33)
996 957 1000 997 m[O6AC12] (23)
1015 976 1015 1020 m[O6AC12] (20); m[C1AC2] (10)
1050 1009 1095 1031 d[H(31)AC2AC1] (10); m[O5AC16] (22)
1109 1066 1112 1110 d[C8AC7AC6] (15); m[O1AC3] (12); m[O3AC6] (12)
1137 1093 d[HAC15AC14] (14); d[HAO6AC12] (14); d[C11AC12AC13] (13)
1145 1101 1159 1157 m[O1AC4] (11)
1170 1125 1172 1172 s[HAC16AO5AC9] (21); s[HAC16AO5AC9] (16); s[HAC16AO5AC9] (29); d[C16H
3
] (27)
1180 1134 1185 1186 d[HAC15AC14] (11); d[HAC11AC3] (10); d[HAO6AC12] (37)
1190 1144 d[HAC5AC1] (22); d[HAC2AC1] (14); d[HAO2AC1] (30)
1198 1152 s[HAC16AO5AC9] (16); d[HAC5AC1] (11)
1207 1160 1213 d[HAC14AC15] (15); d[HAO7AC13] (11)
1216 1169 s[HAC16AO5AC9] (10); d[HAC2AC1] (17)
1225 1178 1223 d[HAO7AC13] (18); d[HAO3AC6] (16)
1244 1196 m[O1AC4] (24); m[O5AC9] (16)
1261 1212 1271 1274 d[HAO2AC1] (19); m[C8AC7] (17); m[C2AC3] (11)
1289 1239 1296 1298 d[HAC15AC14] (10)
1307 1256 1313 d[HAC5AC1] (11); m[O7AC13] (13)
1332 1280 1335 d[HAC11AC3] (23); m[O7AC13] (24); m[C15AC14] (19)
1348 1296 1351 d[HAO6AC12] (13); m[C10AC15] (17)
1377 1324 1365 1365 d[HAC15AC14] (12); d[C9AC4AO1] (19)
1404 1350 d[HAO3AC6] (14); m[C7AC3] (10); m[C5AC1] (14); m[C2AC3] (22); m[C6AC5] (11)
1425 1370 1418 d[HAO7AC13] (31); m[C10AC15] (21)
1434 1379 1439 m[O1AC3] (22); m[O3AC6] (15)
1471 1414 1458 d[HAC16AH(25)] (31); d[C16H
3
] (41)
1479 1422 m[C15AC14] (16); m[C11AC12] (17)
24 T.A. de Toledo et al. / Journal of Molecular Structure 1029 (2012) 2227
in literature [37,38]. On one hand, our calculated C4AC10 bond
connecting rings C and B is 1.471 . In addition, the calculated
bond length of C9AC4 and O4AC8 are 1.366 and 1.231 , respec-
tively. On the other hand, the experimental value between C and B
ring is 1.460 and 1.479 for tithonin-Ac and quercetin, respec-
tively. For quercetin, the experimental bond length of C9AC4 and
O4AC8 are, respectively, 1.357 and 1.267 .
Another important observation from Table 1 is related to the
bond length around carbonyl group. The bond length of C7AC8,
C8AC9, O1AC3 and O1AC4 are 1.464, 1.478, 1.361 and 1.376 ,
respectively. The C9AC4 and O4AC8 double bonds are smaller in
relation to C7AC8, C8AC9, O1AC3 and O1AC4 in the phenyl ring.
These can be explained due the additional bonding electrons pull-
ing the nuclei of neighboring atoms closer together [50]. Another
available important observation is that the p-electrons tends to
locate in the C9AC4 and O4AC8 bonds [32,51].
The torsion angle O1AC4AC10AC11 between AC rings and the
B ring of 3-MQ compound is 19.55, suggesting a non-planar
structure. Such an observation is consistent with the torsion angle
of 7,8-Benzoavone (23.8) and 4
0
-BrA3-OH avones (18.8). In
contrast, the quercetin torsion angle is only 7 that indicates a
fairly planar conformation [37].
The calculated bond angle of C3AO1AC4 and O4AC8AC9 in C
ring are respectively 122.13 and 120.93. On the other hand, in
quercetin compound these bond angles are 120.90 and 120.33.
The small differences in pyrone ring are probably due torsion angle
between AC rings and B ring. This comparison is available due the
fact that the only difference between quercetin and the avonoid
analyzed in our work is the substituent group in C ring. Quercetin
has hydroxyl group in this ring, while metoxyquercetin has the
presence of metoxy in pyrone ring. Our theoretical results are com-
parable with the reported ones.
4.2. Vibrational analysis
The avonoid 3-MQ consists of 35 atomos (this molecule has C1
symmetry) whichproduce 105normal modes per molecule. The 105
normal modes of 3-MQ have been assigned with VEDA software.
Scale factor was used to adjust the theoretical spectra with experi-
mental one. In general, the calculated spectrum is scaled by a semi
empirical factor between 0.96 and 0.99 [4]. It is used to minimize
overestimation factor, such as an incomplete basis set, vibrational
anharmonicity [34]. In the present work, we have used the value
of 0.9613 to adjust our theoretical spectra with experimental data.
The vibrational assignment of the normal modes of the molecule
was performed on the basis of PEDanalysis. Only PEDvalues greater
9% are given. The calculated wavenumbers (in cm
1
), scaled factors,
measured FT-Raman and FT-IR band position (in cm
1
) and assign-
ments with PED are given in Table 2. The nomenclature employed
in the classication of normal modes is as follows: D, d, s, m and
m
asym
stand for deformation out-of-plane, deformation in plane,
torsion, stretching and asymmetric stretching.
Figs. 2 and 3 compare the theoretical (above) and experimental
(below) FT-Raman and FT-IR spectra of 3-MQ, respectively. The
theoretical spectra reported in Figs. 2 and 3 were scaled. In Fig. 2
we observe from the experimental spectrum bands of medium
intensity below 200 cm
1
, which are not observed in the calcu-
lated spectrum. In fact, this region presents, beyond some internal
Table 2 (continued)
x
cal
x
scaled
x
FT-Raman
x
FTIR
Assignment with PED (%)
1497 1439 s[HAC16AO5AC9] (10); d[C16H
3
] (72)
1508 1450 1503 1508 d[HAC2AC1] (12); d[HAO2AC1] (11); m[O3AC6] (11)
1531 1472 1528 s[HAC16AO5AC9] (14); d[C16H
3
] (78)
1542 1482 1552 d[HAC5AC1] (12); d[HAO3AC6] (10); d[C7AC3AO1] (11); m[O2AC1] (11); m[C7AC3] (10)
1571 1510 1565 1560 d[HAC14AC15] (17); d[HAC11AC3] (17); m[O7AC13] (10)
1632 1569 1607 1594 m[C9AC4] (32)
1644 1580 m[C1AC2] (22)
1659 1595 m[C14AC13] (13); m[C9AC4] (15)
1671 1606 m[C14AC13] (15); m[C11AC12] (31)
1679 1614 1624 1616 m[C5AC1] (10); m[C2AC3] (14); m[C6AC5] (19); m[C9AC4] (11)
1727 1660 1650 1647 m[O4AC8] (81)
3035 2918 3078 m
asym
(C16H
3
)
3130 3009 m
asym
(C16H
3
)
3170 3047 3176 m
asym
(C16H
3
)
3197 3073 m[C5AH)] (99)
3204 3080 m[C11AH] (99)
3205 3081 m[C2AH] (99)
3213 3089 m[C14AH] (98)
3268 3142 m[C15AH] (98)
3779 3633 3409 m[O7AH] (100)
3804 3657 m[O3AH] (100)
3824 3676 m[O2AH] (100)
3845 3696 m[O6AH] (100)
D = deformation out-of-plane; s = torsion; d = deformation in-plane; m = stretching; m
asym
= asymmetric stretching.
Fig. 2. Experimental and calculated (scaled) Raman scattering spectra of 3-MQ in
the regions 32002700 and 180020 cm
1
.
T.A. de Toledo et al. / Journal of Molecular Structure 1029 (2012) 2227 25
modes, the external modes that comprises lattice modes of the
crystal. Such kind of modes are not predicted by calculations be-
cause they are performed for isolated molecules. So, beyond the
assignment with PED presented in Table 2, additionally, it is possi-
ble that external modes are gibing contributions to the peaks
appearing in the experimental Raman spectrum for frequencies
lower than 200 cm
1
.
In the region centered at 1600 cm
1
, it is possible to observe
some of the most intense bands of the Raman spectrum. The con-
cordance between the calculated an the experimental spectrum is
very good. In particular we note the presence of the band at
1650 cm
1
, which is associated to a stretching vibration of OAC,
m(O4AC8), belong to the pyrone ring.
Another observation is related to the region above 2900 cm
1
.
In this spectral range it is expected to be observed bands associated
to the stretching of CAH, m(CAH), and to the stretching of OAH,
m(OAH). In general way, the bands associated to m(OAH) have
low intensities in the Raman spectrum, although bands m(CAH)
have relatively high intensities. The only small peak appearing in
the experimental Raman spectrum can be explained as conse-
quence of the kind of detector that was used in the experiment,
which is not very sensitive to the spectral range above 3000 cm
1
.
Now let us discuss the FT-IR spectrum and perform a compari-
son with the FT-Raman spectrum. FT-IR spectrum shows a broad
peak at 3200 cm
1
and at 3400 cm
1
which are attributed to
hydroxyl stretching vibration. This mode is predicted in the range
33793845 cm
1
by DFT calculations. They are pure modes since
their PED contribution is 100%. This broad can additionally indi-
cates the presence of water close to 3-MQ compound.
The aromatic compound shows the presence of CAH stretching
mode above 3000 cm
1
. In the theoretical spectra, the CAH
stretching vibration is observed between 3268 and 3035 cm
1
.
They are almost pure modes since their PED contributions give
more than 98%. On the other hand, this mode was observed in
FT-IR spectrum at 3166 cm
1
. In addition, the asymmetric stretch-
ing of C16H
3
is also observed. FT-Raman spectrum shows the
asymmetric stretching of C16H
3
at 3076 cm
1
.
As already pointed the carbonyl stretching is a very intense
peak observed in the range of 16001800 cm
1
. This spectral
region of infrared and Raman spectroscopy is important because
it is sensitive to substitution effects and the geometry of the mol-
ecule [52]. The p conjugation is observed and it is predicted in
vibrational spectra for carbonyl mode. The carbonyl stretching is
observed for 3-MQ at 1647 cm
1
and 1650 cm
1
in FT-IR and FT
Raman spectra, respectively, as can be seen in Figs. 2 and 3. This
mode was predicted at 1727 cm
1
by DFT calculations.
The aromatic CAC stretching modes are expected to be found
between 1650 and 1200 cm
1
[53]. The C(5)@C(6) stretching vibra-
tions is observed at 1616 cm
1
in FT-IR spectrum and at 1624 cm
1
in FT-Raman spectrum. They are also observed at 1607, 1351 and
1335 cm
1
in FT-Raman spectrum and 1594 and 1552 cm
1
in
FT-IR spectrum. This mode is calculated in the range 1679
1632 cm
1
and between 1542 and 1261 cm
1
.
The in-plane bending of C16H
3
is observed at 1528 and
1172 cm
1
in the FT-Raman and at 1508 and 1172 cm
1
in FT-IR
spectrum. In the theoretical spectrum, this mode is predicted to
be found between 1531 and 1471 cm
1
. The in-plane bending of
C3AO1AC4 is observed at 844 cm
1
in FT-Raman spectrum and
840 cm
1
in the FT-IR spectrum. This mode is calculated at
849 cm
1
by B3LYP/6-31G (d,p) method.
The computed wavenumber by B3LYP/6-31G (d,p) method in
the range 782617 cm
1
are assigned to aromatic out-of-plane
bending of OCCC and CCOC. They are observed in FT-Raman spec-
trum at 731, 721, 687, 674 and 640 cm
1
and at 755, 719, 686, 671
and 640 cm
1
in FT-IR spectrum.
The torsional modes of HOCC were predicted by DFT method at
447, 435, 430, 374, 221, 215, 210 and 150 cm
1
. In the experimen-
tal FT-Raman spectrum only three of these modes are observed.
The wavenumbers predicted at 447, 430 and 374 cm
1
, correspond
to the FT-Raman bands observed at 443, 418 and 380 cm
1
, respec-
tively. On the other hand, they are not observed in the FT-IR
spectrum. The torsional modes of OCCC, COCC and CCCC were pre-
dicted at 447 as well as between 256 and 26 cm
1
. They are also
observed in FT-Raman spectrumat 443, 272, 134, 104 and 96 cm
1
.
5. Conclusions
In the present paper, the avonoid Methoxyquercetin (3-MQ)
has been characterized by FT-IR and FT-Raman spectroscopies.
The geometry parameters and the vibrational wavenumbers of
the 3-MQ molecule were calculated using the B3LYP method with
the 6-31G (d,p) basis set. The optimized structure gives a non-pla-
nar structure. In addition, theoretical results indicate that p conju-
gation tends to be located in the region close to carbonyl group.
Comparisons between calculated geometry and structure obtained
from X-ray diffraction data of other avonoid compounds shows
good agreement. The FT-IR and FT-Raman spectra have been as-
signed and compared with calculated (scaled) vibrational spectra.
The observed and calculated vibrational spectra are found to be
in good agreement. However, small differences between experi-
mental and theoretical data may be attributed to overestimation
factor. Finally, this study has contributed with a description of
vibrational spectra and geometrical parameters analysis of a com-
pound with potential antiviral activity.
Acknowledgements
The authors would like acknowledgement the nancial support
fromFAPEMAT, CNPqandFUNCAP. We wouldliketothankProfessor
E. Dalloglio and J.L.B. Faria from Federal University of Mato Grosso
(UFMT) for computational facilities.
References
[1] R.-W. Jiang, W.-C. Ye, K.-Y. Woo, J. Du, C.-T. Che, P.P.-H. But, T.C.W. Mak, J. Mol.
Struct. 642 (2002) 7784.
[2] S. Birjees Bukhari, S. Memon, M. Mahroof Tahir, M.I. Bhanger, J. Mol. Struct. 892
(2008) 3946.
[3] M. Grazul, E. Budzisz, Coord. Chem. Rev. 253 (2009) 25882598.
[4] C. Corredor, T. Teslova, M.V. Caamares, Z. Chen, J. Zhang, J.R. Lombardi, M.
Leona, Vib. Spectrosc. 49 (2009) 190195.
Fig. 3. Experimental and calculated (scaled) IR absorption spectra of 3-MQ in the
regions 40002800 and 1800400 cm
1
.
26 T.A. de Toledo et al. / Journal of Molecular Structure 1029 (2012) 2227
[5] G. Gattuso, D. Barreca, C. Gargiulli, U. Leuzzi, C. Caristi, Molecules 12 (2007)
16411673.
[6] S. Rubio, J. Quintana, J.L. Eiroa, J. Triana, F. Estvez, Carcinogenesis 28 (2007)
21052113.
[7] E. Middleton, C. Kandaswami, T.C. Theoharides, Pharmacol. Rev. 52 (2000)
673751.
[8] H. Soicke, E. Leng-Peschlow, Planta Med. 53 (1987) 3739.
[9] M.R. Fesen, S. Hirogchi, J. Yung, K.W. Kohn, Y. Pommier, Biochem. Pharmacol.
48 (1994) 595608.
[10] C.Q. Hu, K. Chem, Q. Shi, R.E. Kilkuskie, Y. Cheng, K.H. Lee, J. Nat. Prod. 57
(1994) 4251.
[11] E.E. Deschner, J. Ruperto, G. Wong, H.L. Newmark, Carcinogenesis 12 (1991)
11931196.
[12] D. Tasdemir, M. Kaiser, R. Brun, V. Yardley, T.J. Schmidt, F. Tosun, P. Redi,
Antimicrob. Agents Chemother. 50 (2006) 13521364.
[13] D. Pathak, K. Pathak, A.K. Singla, Fitoterapia 62 (1991) 371388.
[14] R. Landol, R.L. Mower, M. Steiner, Biochem. Pharmacol. 32 (1984) 15251530.
[15] J.C.T. Carvalho, L.P. Ferreira, L.S. Santos, M.J.C. Corra, L.M.O. Campos, J.K.
Bastos, S.J. Sarti, J. Ethnopharmacol. 64 (1999) 173177.
[16] B. Havsteen, Biochem. Pharmacol. 32 (1983) 11411148.
[17] B.E. Leibovitz, J.A. Mueller, J. Optim. Nutr. 2 (1993) 1735.
[18] J.F. Stevens, M. Ivancic, M. Deinzer, E. Wollernweber, J. Nat. Prod. 62 (1999)
392394.
[19] T. Kawakita, M. Kaneko, K. Nornoto, Biol. Pharm. Bull. 19 (1996) 936.
[20] B. Halliwell, J.M.C. Gutteridge, C.E. Cross, J. Lab. Clin. Med. 119 (1992) 598620.
[21] D. Gao, R. Tawa, H. Masaki, Y. Okano, H. Sakurai, Chem. Pharm. Bull. 46 (1998)
13831387.
[22] P. Cos, L. Ying, M. Calomme, J.P. Hu, K. Cimanga, B. Van Poel, L. Pieters, A.J.
Vlietinck, D. Vanden Berghe, J. Nat. Prod. 61 (1998) 7176.
[23] L. Van Hoof, D.A. Vanden Berghe, G.M. Hateld, A.J. Vlietinck, Plant. Med. 50
(1984) 513517.
[24] D.A. Vanden Berghe, A.J. Vlietinck, L. Van Hoof, Bull. Inst. Pasteur 84 (1986)
101147.
[25] N. De Meyer, A. Haemer, L. Mishra, H.K. Pandey, L.A.C. Pieters, D.A. Vanden
Berghe, A.J. Vlietinck, J. Med. Chem. 34 (1991) 736746.
[26] A.M. Palma, Inge Vliegen, Erik De Clercq, Johan Neyts, Med. Res. Rev. (2008)
160.
[27] S. Dimova, R. Mugabowindekwec, T. Willems, M.E. Brewster, M. Noppeb, A.
Ludwigc, M. Jorissend, P. Augustijns, Int. J. Pharm. 263 (2003) 95103.
[28] A.J. Vlietinck, D.A. Vanden Berghe, L. Van Hoof, R. Vrijsen, A. Boey, Prog. Clin.
Biol. Res. 213 (1986) 537540.
[29] J.L. Castrillo, D. Vanden Berghe, L. Carrasco, Virology 152 (1986) 219227.
[30] J.L. Castrillo, L.J. Carrasco, Virology 61 (1987) 33193321.
[31] Y. Tsuchiya, M. Shimizu, Y. Hiyama, K. Itoh, Y. Hashimoto, M. Nakayama, T.
Horie, N. Morita, Chem. Pharm. Bull. 33 (1985) 38813886.
[32] J.P. Abraham, D. Sajan, J. Mathew, I. Hubert Joe, V. George, V.S. Jayakumar, J.
Raman Spectrosc. 39 (2008) 18211831.
[33] N. Subramanian, N. Sundaraganesan, J. Jayabharathi, Spectrochim. Acta, Part A
76 (2010) 259269.
[34] P. Sinha, S.E. Boesch, C. Gu, R.A. Wheeler, A.K. Wilson, J. Phys. Chem. A 108
(2004) 92139217.
[35] W. Kohn, A.D. Becke, R.G. Parr, J. Phys. Chem. 100 (1996) 1297412980.
[36] M.H. Jamrz, J.C. Dobrowolski, J. Mol. Struct. 565566 (2001) 475480.
[37] J. Lameira, C.N. Alves, L.S. Santos, A.S. Santos, R.H. de Almeida Santos, J. Souza
Jr, C.C. Silva, A.B.F. da Silva, J. Mol. Struct.: Theochem. 862 (2008) 1620.
[38] M. Rossi, L.F. Rickles, W.A. Halpin, Bioorg. Chem. 14 (1986) 5569.
[39] T.A. de Toledo, Estudo dos modos vibracionais do avonide 3-
Metoxiquercetina complexado com zinco e cobre, in: Fsica, Universidade
Federal de Mato Grosso, Cuiab, 2010.
[40] C. Lee, W. Yang, R.G. Parr, Phys. Rev. B 37 (1988) 785789.
[41] A.D. Becke, Phys. Rev. A 38 (1988) 30983100.
[42] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
J.A. Montgomery, Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar,
J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A.
Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa,
M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox,
H.P. Hratchian, J.B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann,
O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K.
Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S.
Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K.
Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J.
Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L.
Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M.
Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, J.A.
Pople, Gaussian 03, Revision B.02, Gaussian, Inc., Pittsburgh PA, 2003.
[43] Z. Dhaouadi, M. Nsangou, N. Garrab, E.H. Anouar, K. Marakchi, S. Lahmar, J.
Mol. Struct.: Theochem. 904 (2009) 3542.
[44] G. Keresztury, S. Holly, J. Vaga, G. Besenyei, A.Y. Wang, J.R. During,
Spectrochim. Acta 49A (1993) 20072026.
[45] G. Keresztury, J.M. Calmers, P.R. Grifth (Eds.), Raman Spectrosc: Theory in
Handbook of Vibrational Spectroscopy, vol. 1, John Wiley, New York, 2002.
[46] R. Wysokin ski, K. Hernik, R. Szostak, D. Michalska, Chem. Phys. 333 (2007) 37
48.
[47] D. Michalska, R. Wysokin ski, Chem. Phys. Lett. 403 (2005) 211217.
[48] S. Martens, A. Preu, U. Matern, Phytochemistry 71 (2010) 10401049.
[49] K.E. Heim, A.R. Tagliaferro, D.J. Bobilya, J. Nutr. Biochem. 13 (2002) 572584.
[50] L. Jones, P.W. Atkins, Chemistry: Molecules, Matter and Change, fourth ed.,
2000.
[51] Y. Erdogdu, O. Unsalan, M.T. Gulluoglu, J. Raman Spectrosc. 41 (2010) 820
828.
[52] V. Krishnakumar, M. Sivasubramanian, S. Muthunatesan, J. Raman Spectrosc.
40 (2009) 987991.
[53] N. Subramanian, N. Sundaraganesan, S. Sudha, V. Aroulmoji, G.D. Sockalingam,
M. Bergamin, Spectrochim. Acta, Part A 78 (2011) 10581067.
T.A. de Toledo et al. / Journal of Molecular Structure 1029 (2012) 2227 27