A UV-vis study of the effects of alcohols on formation and stability of Mn(por)(O)(OAc) complexes

Article abstract of DOI:10.1016/j.saa.2012.01.001

Interactions of three different (acetato) (tetraarylporphyrinato) manganese (III) Mn^III(por) with tetra-n-butylammonium hydrogen monopersulfate (n-Bu₄NHSO₅), in the presence of excess tetra-n-butylammonium acetate (n-Bu₄NOAc) and in the absence or presence of various alcohols (alcohols = CH₃OH, C₂H ₅OH, i-C₃H₇OH, t-C₄H₉OH) in CH₂Cl₂, were monitored by their UV-vis spectral changes, under identical conditions, at room temperature. (Acetato) (tetrakispentafluorophenylporphyrinato) manganese (III) Mn^III(tpfpp) (OAc) and (acetato) (tetramesitylporphyrinato) manganese (III) Mn ^III(tmp)(OAc) produced their corresponding high valent Mn(tpfpp)(O)(OAc) and Mn(tmp)(O)(OAc) both in the absence or presence of alcohols. Whereas, (acetato) (tetraphenylporphyrinato) manganese (III) Mn ^III(tpp)(OAc) only generated Mn(tpp)(O)(OAc) in the presence of less bulky alcohols. In the absence of alcohols or in the presence of t-C ₄H₉OH, the UV-vis spectra displayed a very weak sign of formation of Mn(tpp)(O)(OAc) complex. It was observed that alcohols generally increased the rate of formation of Mn-oxo species in accordance with their acidity or hydrogen bonding strength, and enhanced the stability of Mn-oxo complexes, as their size increases. Attempts are made to explain these effects. A mechanistic scheme is also suggested for the decomposition of HSO ₅^- to O₂ and HSO₄^-, through the formation and dimerization of Mn-oxo species.

Full text of DOI:10.1016/j.saa.2012.01.001

Spectrochimica Acta Part A 91 (2012) 360–364
Contents lists available at SciVerse ScienceDirect
Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa
A UV–vis study of the effects of alcohols on formation and stability of
Mn(por)(O)(OAc) complexes
Daryoush Mohajer∗, Maryam Jahanbani
Department of Chemistry, Shiraz University, Shiraz 71454, Iran
a r t i c l e i n f o
a b s t r a c t
Interactions of three different (acetato) (tetraarylporphyrinato) manganese (III) MnIII(por) with
tetra-n-butylammonium hydrogen monopersulfate (n-Bu4NHSO5), in the presence of excess tetra-
n-butylammonium acetate (n-Bu4NOAc) and in the absence or presence of various alcohols
(alcohols = CH3OH, C2H5OH, i-C3H7OH, t-C4H9OH) in CH2Cl2, were monitored by their UV–vis spectral
changes, under identical conditions, at room temperature. (Acetato) (tetrakispentafluorophenylpor-
phyrinato) manganese (III) MnIII(tpfpp)(OAc) and (acetato) (tetramesitylporphyrinato) manganese (III)
MnIII(tmp)(OAc) produced their corresponding high valent Mn(tpfpp)(O)(OAc) and Mn(tmp)(O)(OAc)
both in the absence or presence of alcohols. Whereas, (acetato) (tetraphenylporphyrinato) manganese
(III) MnIII(tpp)(OAc) only generated Mn(tpp)(O)(OAc) in the presence of less bulky alcohols. In the absence
of alcohols or in the presence of t-C4H9OH, the UV–vis spectra displayed a very weak sign of formation
of Mn(tpp)(O)(OAc) complex. It was observed that alcohols generally increased the rate of formation
of Mn–oxo species in accordance with their acidity or hydrogen bonding strength, and enhanced the
stability of Mn–oxo complexes, as their size increases. Attempts are made to explain these effects. A
Article history:
Received 24 July 2011
Received in revised form 2 January 2012
Accepted 2 January 2012
Keywords:
Manganese porphyrin
UV–vis
Alcohols
O ligand
−
mechanistic scheme is also suggested for the decomposition of HSO5 to O2 and HSO4−, through the
formation and dimerization of Mn–oxo species.
© 2012 Published by Elsevier B.V.
1. Introduction
Mn(tpfpp)(O)(OAc), which was not possible by n-Bu4NIO4 [8]. A
mechanistic scheme has also been tentatively proposed, for the
Generation and reactivity of high valent manganese–oxo por-
phyrin complexes, as the active site models of cytochrome P-450
enzymes, have attracted attention for over two decades [1–7]. An
important objective in the study of such reactive intermediates is
to elucidate the nature of the factors that may determine their
chemical properties. However, gaining insights into the reactiv-
ity pattern of the manganese–oxo complexes of porphyrin, has
often been hampered by their transient nature. Recently, we have
shown that alcohols can play a critical role in defining the stability
and reactivity of two different [Mn(por)(O)(im)]+ species, formed
by tetra-n-butylammonium periodate (n-Bu4NIO4), as a mild oxi-
dant [8]. In this study we have compared the generation and
stability of three stereoelectronically different Mn(por)(O)(OAc)
complexes (Fig. 1) by employing tetra-n-butylammonium hydro-
gen monopersulfate (n-Bu4NHSO5), as a strong oxidant, and by
using the oxidatively stable OAc− axial ligand, in the presence or
absence of various alcohols, under identical conditions. In partic-
ular, this work has provided new conditions for the generation of
first time, for catalytic decomposition of HSO5− to O2 and HSO4− by
mediation of MnIII(por), through formation and possible coupling
of high valent Mn(por)(O)(OAc) complex.
2. Experimental
2.1. Materials
All the solvents were distilled under nitrogen prior to the use.
Dichloromethane was purified by distillation over P2O5 and/or
CaH2 and stored over molecular sieves (Linde 4A). Methanol
(99.8%), ethanol (99.6%), and i-propanol (99.5%) were purchased
from Merck or Fluka. t-Butanol (99.4%), was obtained from Aldrich.
Deionized, double-glass distilled water was used for all the experi-
ments. A constant temperature bath was employed to maintain the
temperature at 25 2 ◦C.
The free base porphyrin ligands, H2TPP [9], H2TMP [10] and
H2TPFPP [11] were prepared in accordance with the previously
reported methods. Manganese was inserted by standard routes
[12,13]. The synthesis of tetra-n-butylammonium peroxymono-
sulfate was achieved by the known procedures [14,15]. Since the
oxidizing ability of n-Bu4NHSO5 diminishes with time, the freshly
∗
Corresponding author. Tel.: +98 711 6137359; fax: +98 711 2280926.
E-mail addresses: dmohajer@chem.susc.ac.ir,
daryoushmohajer@yahoo.com (D. Mohajer).
1386-1425/$ – see front matter © 2012 Published by Elsevier B.V.
doi:10.1016/j.saa.2012.01.001

D. Mohajer, M. Jahanbani / Spectrochimica Acta Part A 91 (2012) 360–364
361
Ar
R2
R3
OAc
N
N
R4
Ar
Mn
Ar =
Ar
N
N
R2
R3
Ar
[MnIII (por)]
R4
R3
R2
[MnIII(tpp)(OAc)]
[MnIII(tmp)(OAc)]
[MnIII(tpfpp)(OAc)]
H
CH3
F
H
H
F
H
CH3
F
Fig. 1. (Acetato) (tetraarylporphyrinato) manganese (III) complexes used in this study.
formation of six coordinate [MnIII(tpfpp)(OAc)2]− complex in equi-
librium with MnIII(tpfpp)(OAc). Addition of n-Bu4NHSO5 to this
solution resulted in a new Soret band (ꢀmax = 420 nm), concomi-
tant with complete disappearance of 466 nm band, in ca. <45 s.
The 420 nm band, which is related to the formation of high valent
Mn(tpfpp)(O)(OAc) [17,18], remained virtually intact for ca. 2000 s,
and then decayed slowly with reappearance of the 466 nm band.
However, the 420 nm band disappeared completely after 24 h and
the 466 nm ba−nd was mostly recovered, indicating total decompo-
sition of HSO5 and some degradation of the MnIII(por).
prepared oxidant was refrigerated and used within three days. Cau-
tion: n-Bu4NHSO5 should be considered as a potentially explosive
compound. n-Bu4NOAc was prepared by using the known method
[16].
2.2. General procedure
Stock CH2Cl2 solutions of MnIIIPor (2 ml, 1.2 × 10−5 M), n-
Bu4NOAc (48 ␮L, 0.25 M) and n-Bu4NHSO5 (1–96 ␮L, 0.25 M) were
added into a 1-cm UV cell. If alcohol was needed, then 50 ␮L was
added to the UV-cell before the addition of n-Bu4NHSO5. For this
study, the best molar ratio of MnIII(por)/n-Bu4NOAc/n-Bu4NHSO5
was found to be 1/500/100.
Changing solely the molar ratio of HSO5−/MnIII(por), causes a
dramatic effect on the formation rate and the lifetime of Mn–oxo
complex (Fig. 3). For HSO5−/MnIII(por) = 10, complete conver-
sion of MnIII(por) to Mn–oxo complex occurred in ca. 1200 s,
while for HSO5−/MnIII(por) ≥ 300 it happened instantly. For all
HSO5−/MnIII(por) ≥ 10, after complete conversion of MnIII(por) to
Mn–oxo, the intensity of the 420 nm band remained virtually
unchanged for a limited period of time, increasing from ca. 300 s
(HSO5−/MnIII(por) = 10) to >10,000 s (HSO5−/MnIII(por) ≥ 300).
These results indicate that both the formation rate and the lifetime
of Mn–oxo complex enhance as HSO5−/MnIII(por) ratio increases.
It may also be concluded that, in the time span wherein the inten-
sity of the 420 nm band is fixed, the system is under a steady state
condition, and the rate of generation of Mn–oxo complex and its
decay rate to MnIII(por) and O2 are equal.
The electronic absorption spectra were recorded on
MultiSpect-1501 Shimadzu spectrophotometer.
a
3. Results and discussion
3.1. MnIII(tpfpp)(OAc)
The UV–vis spectra for interaction of MnIII(tpfpp)(OAc) with
n-Bu4NHSO5 in the presence of n-Bu4NOAc under MnIII(por)/n-
Bu4NOAc/n-Bu4NHSO5 molar ratio of 1/500/100 in CH2Cl2, at room
temperature, are presented in Fig. 2. Addition of n-Bu4NOAc to
CH2Cl2 solution of MnIII(tpfpp)(OAc) (Soret, ꢀmax = 474 nm) gave
a broad Soret band (ꢀmax = 466 nm) with a shoulder, reflecting the
Furthermore, it was found that the intensities of 466 and 420 nm
bands are inversely related in the course of decomposition of
HSO5−, in the presence of MnIII(tpfpp)(OAc), under the molar ratio
of HSO5−/MnIII(por) = 10 (Fig. S1). After complete decomposition
1.2
0.8
0.4
0
474
a
420
c
466
b
350
450
550
650
Wavelength / nm
Fig. 2. UV–vis spectra for interaction of MnIII(tpfpp)(OAc) with n-Bu4NHSO5:
MnIII(tpfpp)(OAc) (2.4 × 10−5 mmol) in CH2Cl2 (2 mL, 1.2 × 10−5 M) (a); (a) + n-
Bu4NOAc (1.2 × 10−2 mmol) (b); (b) + n-Bu4NHSO5 (2.4 × 10−3 mmol) (c), at
25 2 ◦C.
Fig. 3. Changes in the Soret band intensities of Mn(tpfpp)(O)(OAc) (ꢀmax = 420 nm)
versus time/s, for three different HSO5−/MnIII(tpfpp)(OAc) molar ratios (i.e., 10, 100,
300), at 25 2 ◦C.

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D. Mohajer, M. Jahanbani / Spectrochimica Acta Part A 91 (2012) 360–364
−
of HSO5 and/or loss of the 420 nm band, the 466 nm band reap-
peared, with virtually no loss of intensity.
formation of the high valent Mn(tpfpp)(O)(OAc) and HSO4−. It is
noteworthy that since the O O bond cleavage is sensitive to the
acidity of the alcohols, it is expected to be heterolytic rather than
homolytic [24]. The resulting Mn–oxo species may be formally rep-
resented by two ␣ valence resonance ꢁ forms, MnV(tpfpp)(O)(OAc)
(III) and MnIV(tpfpp)(O•)(OAc) (IV) [25]. Third, possible coupling
of species IV, through radical O• ligand, yields the transient dinu-
clear complex (V) with a ␮-peroxo bridging group. The resulting
dimeric species (V) is expected to have a skew structure, due to the
repulsive forces among the lone pairs of the peroxy O O bridge and
their adjacent Mn O bonds, similar to H2O2 [26]. Accordingly, the
MnIV(por) moieties in the dinuclear compound (V) may clash and
make it highly unstable. It should be noted that, hydrogen bonding
of alcohols to the lone pairs of O O bridging group may also reduce
the stability of the dinuclear complex. Fourth, homolytic breakage
of the presumably tense O O and either of the Mn O bonds of
(V) may result in several species, (I), (IV) and (VI). Fifth, complex
(VI) which might be in resonance with (VII) can very rapidly and
reversibly release O2 and give the starting MnIII(por) (I) species, and
then the catalytic cycle closes.
The dimerization of (IV) is expected to be the rate determin-
ing step in Scheme 1, because the lifetime of Mn–oxo species
increases with both the steric bulk of the solvating alcohols, and
the porphyrin ligand (see below). It appears that, these findings
may provide a clue to the understanding of the long-standing ques-
tion concerning the observed high stability and/or low reactivity of
Mn–oxo porphyrins in the presence of excess Bu4NOH [27,28]. As
suggested for the alcohols, possible hydrogen bonding of Bu4NOH
with the O ligand of Mn–oxo porphyrins can cause steric constrains
at the Mn–oxo active site, and consequently hinders its dimeriza-
tion or reaction with a substrate.
Consistent with O2 evolution from Mn(por)(O) species [19,20],
these findings strongly s−uggest that MnIII(tpfpp)(OAc) catalyzes the
decomposition of HSO5 to O2 and HSO4−, through the formation
of intermediate Mn(tpfpp)(O)(OAc) complex. It also appears that
the rate of formation of Mn–oxo species is greater than its decay
rate to MnIII(por) complex and O2 (see below).
3.2. MnIII(tpfpp)(OAc)/alcohols
Th−e UV–vis spectra for interaction of MnIII(tpfpp)(OAc) with
HSO5 in the presence of n-Bu4NOAc and CH3OH (Fig. S2) indicate
the generation of Mn(tpfpp)(O)(OAc) (ꢀmax = 418 2 nm) [17,18].
Similar spectral changes were also observed in the presence of
C2H5OH, i-C3H7OH and t-C4H9OH. Changes in the intensity of
Mn–oxo Soret bands were monitored, in the absence and pres-
ence of various alcohols, under identical conditions, over a period
of 2000 s (Fig. S3). All the intensity curves display a rather sharp
rise (reflecting a rapid Mn–oxo formation), and then descend very
gently (reflecting a rather slow Mn–oxo decay). Consideration
of the relative slopes of Mn–oxo Soret intensity curves (Fig. S3)
indicates that formation of Mn–oxo complex in the presence of
alcohols increases in the order CH3OH > C2H5OH > i-C3H7OH ∼ t-
C4H9OH ∼ no alcohol. Accordingly, alcohols with smaller size
and/or stronger hydrogen bonding ability or acidity [8,21,22], are
more effective in generating Mn–oxo complex.
It appears that alcohols through hydrogen bonding with the
coordinated HSO5 (Fig. S4a), can facilitate heterolytic cleavage of
−
the O O bond, leading to rapid formation of Mn–oxo complex and
HSO4−. Furthermore, it seems that the order of stability of Mn–oxo
species in the absence or presence of various alcohols decreases as,
no alcohol < CH3OH < C2H5OH < i-C3H7OH < t-C4H9OH (Fig. S3). It is
noteworthy that, in the presence of bulky t-C4H9OH, the Mn–oxo
complex was stable even after 24 h. These findings suggest that
hydrogen bonding of alcohols to O ligand of Mn–oxo complex (Fig.
S4b) increases the stability of Mn–oxo species, and apparently alco-
hols of larger molecular size are more effective in this respect [8].
Two possible pathways may be envisaged for the transformation
of Mn(tpfpp)(O)(OAc) complex to MnIII(tpfpp)(OAc) and O2. These
are (i) direct cleavage of the Mn O bond and (ii) initial coupling of
the Mn–oxo species and formation of a transient dinuclear complex
containing an O O bridging group, followed by its collapse to O2
and MnIII(por). However, the direct Mn O bond breakage pathway
may be ruled out, because Mn O bond is expected to be weakened
by hydrogen bonding with alcohols [23], and accordingly it should
be less stable in the presence of alcohols than in their absence.
Clearly, this is in complete contrast with the observed greater sta-
bility of Mn(tpfpp)(O)(OAc) in the presence of alcohols. On the
contrary, the dimerization pathway of Mn–oxo complex is expected
to become hindered by hydrogen bonding of Mn–oxo species with
alcohols. Furthermore, bulkier alcohols should be able to stabi-
lize Mn–oxo complex to a greater extent. Thus, the dimerization
pathway seems to comply well with our findings.
3.4. MnIII(tpp)(OAc)/alcohols
Treatment of MnIII(tpp)(OAc) with n-Bu4NHSO5 in the presence
of n-Bu4NOAc in CH2Cl2 containing CH3OH led to distinct spectral
changes (Fig. S5), similar to those of Mn(tpfpp)(OAc). A new Soret
band (ꢀmax = 422 nm), due to the formation of Mn(tpp)(O)(OAc)
[17,29], rapidly appeared (200 s). In the absence of CH3OH, addition
of n-Bu4NHSO5 caused complete degradation of MnIII(tpp)(OAc) in
ca. 3000 s, with a very weak sign of formation of Mn(tpp)(O)(OAc).
Consideration of the slopes of the formation and decay
traces of Mn(tpp)(O)(OAc) (ꢀmax = 422 nm), in the absence
or presence of various alcohols (Fig. S6), suggests that the
formation rate of Mn(tpp)(O)(OAc) increases in the order
CH3OH > C2H5OH ꢀ i-C3H7OH ꢀ t-C4H9OH ∼ no alcohol. On the
contrary, the stability of Mn(tpp)(O)(OAc) increases in the order i-
C3H7OH > C2H5OH ꢀ CH3OH ꢀ t-C4H9OH ∼ no alcohol. These find-
ings are similar to those obtained for Mn(tpfpp)(O)(OAc). However,
apparently, t-C4H9OH acts quite differently in the presence of
Mn(tpp)(O)(OAc), and is not able to display effectively its hydrogen
bonding capability.
3.5. MnIII(tmp)(OAc)
3.3. Suggested mechanism
Similar to MnIII(tpfpp)(OAc), in the absence of alcohols,
interaction of MnIII(tmp)(OAc) with n-Bu4NHSO5, in the pres-
ence of n-Bu4NOAc led to the formation of Mn(tmp)(O)(OAc)
(ꢀmax = 420 2 nm) (Fig. S7) [2,27]. However, the reaction
was slower and did not reach completion after 24 h. Com-
plete conversion of MnIII(tmp)(OAc) to Mn(tmp)(O)(OAc), in
short times (<100 s), required much higher molar ratio of n-
Bu4NHSO5/MnIII(tmp)(OAc) (ca. ≥800) (Fig. S7, inset). On the other
hand, Mn(tmp)(O)(OAc) displayed a much longer lifetime than
Mn(tpfpp)(O)(OAc).
A
multistep mechanism is tentatively proposed for O2
−
evolution from HSO5
decomposition, in the presence of
MnIII(tpfpp)(OAc) (I), Scheme 1. First, reversible coordination of
HSO5− to MnIII(tpfpp)(OAc) gives the six coordinate anionic species
[MnIII(tpfpp)(OAc)(HSO5)]− (II). Second, prot−on transfer may occur
from the coordinated oxygen atom of HSO5 to its adjacent oxy-
gen atom. This process is facilitated by hydrogen bonding of the
proton to an O donor site (Fig. S4a). This s−tep is then followed by
heterolytic cleavage of O O bond of HSO5 ligand, leading to the

D. Mohajer, M. Jahanbani / Spectrochimica Acta Part A 91 (2012) 360–364
363
O2
(I)
MnIII
O
2
O
-
2HSO5
H
MnIII
OAc
_
(VII)
SO3
O
OAc
O
+2OAc- -2OAc-
OAc
_
O
O
MnIII
MnIII
OAc
2
2
MnIV
OAc
(VI)
(I)
OAc
(II)
fast
O
OAc
-
2HSO4
MnIV
O
O
O
r.d.s
fast
MnV
MnIV
MnIV
2
2
OAc
(V)
OAc
(III)
OAc
(IV)
Scheme 1. Proposed mechanism for catalytic decomposition of HSO5 by MnIII(por).
−
of free HSO5− by bulky t-C4H9OH, hindering its coordination to the
bulky MnIII(tmp)(OAc).
3.6. MnIII(tmp)(OAc)/alcohol
Interaction of MnIII(tmp)(OAc) with n-Bu4NHSO5 in the pres-
ence of n-Bu4NOAc and CH3OH or t-C4H9OH led to the formation
of Mn(tmp)(O)(OAc). However, formation of Mn(tmp)(O)(OAc) was
not complete even after 24 h. Consideration of the intensity changes
of 420 2 nm band versus time, in the absence and presence of
CH3OH and t-C4H9OH, in the first 10,000 s, indicates that these
alcohols play different roles in the generation of Mn(tmp)(O)(OAc)
(Fig. 4).
In the presence of non-coordinating t-C4H9OH and also in the
absence of alcohol, the intensity of 420 2 nm band increased
with time, suggesting increased formation of Mn(tmp)(O)(OAc).
However, the greater slope of the line (a) than that of (c)
(Fig. 4), indicates that t-C4H9OH reduces the formation rate of
Mn(tmp)(O)(OAc). This behavior is probably due to the solvation
In the presence of coordinating CH3OH, a relatively sharp
increase in the intensity of 420 2 nm band was initially (ca.
<1000 s) observed. The intensity of the 420 2 nm band then
remained almost unchanged, after ca. >3000 s. This suggests that
the system has reached a steady state condition, in which the
formation and the decay rates of Mn(tmp)(O)(OAc) are almost
identical. The higher intensity of the 420 2 nm band in the pres-
ence of CH3OH than in its absence, at the start of the reaction
(Fig. 4a and b), seems to be in accord with the view that CH3OH
can increase the rate of formation of Mn(tmp)(O)(OAc), by hydro-
gen bonding to the coordinated HSO5−, facilitating the heterolytic
cleavage of its O O bond. On the contrary, the observed lower
intensity of 420 2 nm band in the presence of CH3OH at the longer
times (ca. 6500 s), is perhaps due to the effect of reversible coor-
dination of CH3OH to MnIII(tmp)(OAc), and possible formation of
[MnIII(tmp)(OAc)(CH3OH)] and [MnIII(tmp)(CH3OH)2]+ complexes,
with no coordination site available for bonding of HSO5−. Thus,
CH3OH can reduce the effective concentration of the five coordinate
MnIII(tmp)(OAc) complex. Consequently, at the longer times, when
all the available MnIII(tmp)(OAc) species are converted to the cor-
responding Mn–oxo complex, the intensity of the 420 2 nm band
should be smaller in the presence of CH3OH than in its absence. It
appears that the relatively very slow rate of formation and decay of
Mn(tmp)(O)(OAc) may allow the coordination effect of CH3OH to
MnIII(tmp)(OAc) to become pronounced only at the longer times.
Apparently, for MnIII(tpp)(OAc) and MnIII(tpfpp)(OAc), with rela-
tively rapid formation and decay rates of Mn–oxo, the effect of
coordination of CH3OH to the MnIII(por) is not recognizable.
4. Conclusions
Fig. 4. Formation traces of MnIII(tmp)(O)(OAc) at 420 nm band for reaction
of MnIII(tmp)(OAc) (2.4 × 10−5 mmol)/n-Bu4NOAc (1.2 × 10−2 mmol)/n-Bu4NHSO5
(2.4 × 10−3 mmol) in CH2Cl2 (2 mL)/alcohol (50 ␮L) [without alcohol (a); CH3OH (b);
t-C4H9OH (c)], at 25 2 ◦C.
Interaction of various MnIII(por) with n-Bu4NHSO5 in the
presence of an excess n-Bu4NOAc leads to the formation of
Mn(por)(O)(OAc), in the absence or presence of alcohols, at

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room temperature. Alcohols generally speed up the formation
of Mn(por)(O)(OAc), through hydrogen bonding with the coordi-
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−
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collapse of a transient dinuclear intermediate complex, with O
O
bridging group. A plausible mechanism is proposed for catalytic
decomposition of HSO5 by MnIII(por).
−
Acknowledgment
The authors are thankful for financial supports from Shiraz Uni-
versity Research Council.
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Supplementary data associated with this article can be found, in
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