Synthesis and properties of a new (octaethylporphyrinato)-manganese(III)–pyridinyl-substituted pyrrolidinofullerene dyad

Article abstract of DOI:10.1134/S1070428016100213

The formation of a porphyrin–fullerene dyad from 2′-(pyridin-4-yl)-5′-(pyridin-2-yl)-1′-(pyridin-3-ylmethyl)-2′,5′-dihydro-1′H-pyrrolo[3′,4′: 1,9](C₆₀-I_h)[5,6]fullerene and (2,3,7,8,12,13,17,18-octaethylporphyrinato) manganese(III) with axial chloride ligand has been studied on a quantitative level with the goal of obtaining supramolecules possessing biological activity. Preliminarily, the reaction of manganese(III) porphyrin with pyridine has been studied. The donor–acceptor dyads are formed either instantaneously and reversibly (pyridine) or slowly and irreversibly (substituted fullerene). In both cases, the reaction is a one-step process for which thermodynamic and kinetic parameters have been determined. The results can be used to optimize conditions for the synthesis of porphyrin–fullerene dyads. The obtained dyads have been characterized by spectral data and stability constants.

Full text of DOI:10.1134/S1070428016100213

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2016, Vol. 52, No. 10, pp. 1503–1508. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © E.N. Ovchenkova, N.G. Bichan, T.N. Lomova, 2016, published in Zhurnal Organicheskoi Khimii, 2016, Vol. 52, No. 10,
pp. 1509–1515.
Synthesis and Properties of a New (Octaethylporphyrinato)-
manganese(III)–Pyridinyl-Substituted Pyrrolidinofullerene Dyad
E. N. Ovchenkova, N. G. Bichan, and T. N. Lomova*
Krestov Institute of Solution Chemistry, Russian Academy of Sciences, ul. Akademicheskaya 1, Ivanovo, 153045 Russia
*
e-mail: tnl@isc-ras.ru
Received April 25, 2016
Abstract—The formation of a porphyrin–fullerene dyad from 2′-(pyridin-4-yl)-5′-(pyridin-2-yl)-1′-(pyridin-3-
ylmethyl)-2′,5′-dihydro-1′H-pyrrolo[3′,4′:1,9](C60-I )[5,6]fullerene and (2,3,7,8,12,13,17,18-octaethylpor-
h
phyrinato)manganese(III) with axial chloride ligand has been studied on a quantitative level with the goal of
obtaining supramolecules possessing biological activity. Preliminarily, the reaction of manganese(III) porphyrin
with pyridine has been studied. The donor–acceptor dyads are formed either instantaneously and reversibly
(
pyridine) or slowly and irreversibly (substituted fullerene). In both cases, the reaction is a one-step process for
which thermodynamic and kinetic parameters have been determined. The results can be used to optimize
conditions for the synthesis of porphyrin–fullerene dyads. The obtained dyads have been characterized by
spectral data and stability constants.
DOI: 10.1134/S1070428016100213
Resistance of infectious agents to antibiotics and
inability of pharmaceutical industry to create new anti-
biotic strains are growing problems in health protec-
tion [1, 2]. Nowadays, considerable attention is given
to the synthesis of new antibacterial agents [3–6].
Among the latter, of particular interest are porphyrin
complexes [7–9] due to their ability to act as photo-
sensitizers. Antimicrobial photodynamic therapy, i.e.
photodynamic inactivation of microorganism, is a new
alternative method for the treatment of microbial
infections [10–12].
The role of manganese in functioning of such enzymes
as superoxide dismutase, glutamine synthetase, and
arginase has been revealed [13]. Antibacterial prop-
erties of manganese(III) tetraphenylporphyrin against
gram positive Staphylococcus aureus have been report-
ed [14]. Manganese(III) complexes with porphyrins
containing 4-aminophenyl and N-phenylureido groups
in the meso positions show considerably higher anti-
bacterial and antifungal activity than their unsubstitut-
ed analogs against gram negative Escherichia coli and
Pseudomonas aeruginosa, gram positive Bacillus
subtilis, Aspergillus oryzae, and Candida albicans
[15]. At present, not only porphyrins and their metal
complexes but also supramolecular systems based
thereon with additional pharmacophoric fragments are
Interest in manganese porphyrins that are subjects
of the present study is determined by biological im-
portance of manganese. Manganese is necessary for
normal physiological development of living organisms.
N
Cl Et
Et
Et
N
Mn
N
N
Et
N
N
Et
N
Et
Et
Et
N
(
Cl)MnOEtPor
Py C
3 60
1
503

1
504
OVCHENKOVA et al.
position and intensity of the main absorption maxima
A
360
A
3
71
of (Cl)MnOEtPor with retention of isosbestic points.
The Soret band shifted red by 11 nm, the charge-
transfer band (π→d transition) shifted blue by 2 nm,
and the blue shift of the Q band was 14 nm (Fig. 1).
The spectrophotometric titration curve was a straight
line with a bent at the minimum optical density, which
corresponds to a one-step process. Figure 1 shows the
transition area.
0
0
0
.48
.43
.38
0
.5
.4
.3
.2
.1
.0
4
73
0
2
4
6
c
Py, M
0
0
0
0
The slope of the logarithmic dependence of I versus
cPy (Fig. 2) is close to unity, which suggests 1:1 com-
plex formation; K = 0.90±0.03 L/mol (Scheme 1). The
product is a donor–acceptor complex of pyridine with
5
48
62
5
(
Cl)MnOEtPor (see below).
3
50
400
450
500
550
λ, nm
Scheme 1.
K
Fig. 1. Variation of the electronic absorption spectrum of
Cl)MnOEtPor in toluene upon addition of pyridine (0 to
M). The insert shows the spectrophotometric titration curve
at λ 360 nm.
(
Cl)MnOEtPor
+
Py
(Cl)(Py)(MnOEtPor)
(
7
The spectrophotometric titration data for the reac-
tion of (Cl)MnOEtPor with pyridine (Fig. 1) suggest
axial coordination of pyridine molecule to Mn(III)
without elimination of the chloride ion. This coordina-
tion mode reduces deviation of the manganese atom
from the porphyrin macrocycle plane and is respon-
sible for the blue shift of the Q band in the electronic
absorption spectrum. The observed spectral variations
are consistent with published data. According to [18],
addition of pyridine to a benzene solution of (acetoxo)-
logI
0
0
0
.6
.4
.2
–
0.6
–0.2
0.2
0.6
–
0.2
0.4
0.6
0.8
logcPy
–
–
–
(
2,8,12,18-tetrabutyl-3,7,13,17-tetramethyl-5,15-di-
phenylporphyrinato)manganese(III) induces a blue
shift of the charge-transfer band.
Fig. 2. Logarithmic dependence of I on the pyridine concen-
tration cPy for the reaction of (Cl)MnOEtPor with pyridine
at 298 K; tanα = 0.98 (R = 0.99).
The product structure was also optimized by PM3
quantum chemical simulation of (Cl)MnOEtPor and
pyridine molecules and the corresponding 1:1 donor–
acceptor dyad. The latter was calculated with different
mutual orientations of the chloride ion and pyridine
molecule. Figure 3 shows the optimized structures of
(Cl)MnOEtPor and complexes (Cl)(Py)MnOEtPor
(heats of formation ‒110.03 and ‒46.01 kcal/mol) with
trans and cis orientations of the chloride ion with
respect to the pyridine molecule. The complex with
trans orientation of the axial ligands (Fig. 3, b) was
characterized by the lowest heat of formation and was
assumed to be the most probable. The calculations
showed that the manganese atom in the complex
(Cl)(Py)MnOEtPor deviates from the plane formed
2
extensively studied. For example, the activity of ful-
lerene systems against E. coli and herpes viruses, in-
cluding cytomegalovirus, has been reported [16, 17].
We have synthesized supramolecular systems from
(
chloro)(2,3,7,8,12,13,17,18-octaethylporphyrinato)-
manganese(III) [(Cl)MnOEtPor] and an organic base,
′-(pyridin-4-yl)-5′-(pyridin-2-yl)-1′-(pyridin-3-yl-
methyl)-2′,5′-dihydro-1′H-pyrrolo[3′,4′:1,9](C -I )-
2
6
0
h
[
5,6]fullerene (Py C ) and characterized them by
3 60
physicochemical methods. Taking into account that
Py C binds to manganese(III) through pyridine
3
60
residues, it was necessary to study the reaction of
Cl)MnOEtPor with pyridine. The equilibrium in this
(
by the porphyrin nitrogen atoms (N ) by 0.75 Å
4
system was achieved immediately after mixing the
reactants; the electronic spectra showed changes of the
and that the corresponding deviation in trans-
(Cl)(Py)MnOEtPor is 0.26 Å.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 10 2016

SYNTHESIS AND PROPERTIES OF A NEW (OCTAETHYLPORPHYRINATO)...
1505
(
a)
(b)
(c)
Fig. 3. Optimized (PM3) structures of (a) (Cl)MnOEtPor and its complexes with pyridine with (b) trans and (c) cis orientations of the
axial ligands.
The formation of (Cl)(Py)MnOEtPor was also
monitored by variation of characteristic IR absorption
bands of the porphyrin macrocycle. Appreciable
changes, in particular a high-frequency shift by 4‒
absorbance at λmax 468 nm with a distinct isosbestic
point (Fig. 4). The electronic absorption spectrum of
the product corresponds to the manganese(III) porphy-
rin chromophore. As we showed previously [21] by
Beer–Lambert measurements, neither aggregation nor
other processes were observed in the system Py C –
–
1
–1
6
cm , were observed in the region 1600–1640 cm
typical of skeletal vibrations. This shift may be ration-
alized by movement of the manganese atom toward the
macrocycle plane. It is known that skeletal vibration
frequencies of porphyrins are sensitive to chemical
modifications such as functional substitution and axial
coordination [19]. The C‒H stretching frequencies of
the ethyl groups change only slightly upon formation
of (Cl)(Py)MnOEtPor. The IR spectrum of
3
60
toluene in the absence of metal porphyrin.
By kinetic study of the reaction of (Cl)MnOEtPor
with Py C at different concentrations of the latter we
3
60
determined first orders of the reaction with respect to
both reactants (Figs. 5, 6) and calculated effective first-
order rate constants k (see table) and bimolecular rate
ef
constants k [Eq. (1)].
(
Cl)(Py)MnOEtPor contained new bands at 1741,
–
∂c(Cl)MnOEtPor/∂τ = kc(Cl)MnOEtPor c
Py3C60
3 60
1
3
702, 1405, 1220, 1180, 922, 876, 716, 702, and
98 cm due to vibrations of N-bonded pyridine [20];
–2
(1)
–
1
= (4.07±0.14)×10 c
(Cl)MnOEtPor
cPy33C660.
no such bands were observed in the spectrum of
Cl)MnOEtPor. The vibrational frequencies of coor-
Thus, the kinetics of the reaction of (Cl)MnOEtPor
with Py C corresponds to irreversible bimolecular
reaction with the formation of 1 : 1 complex
(
–
1
3
60
dinated pyridine were higher by ~5–35 cm than those
in the spectrum of free pyridine. A new weak band at
–
1
4
68 cm in the spectrum of (Cl)(Py)MnOEtPor was
A
468
473
assigned to the Mn‒N bond [19].
Py
Analogous spectral variations were observed for the
reaction of (Cl)MnOEtPor with Py C , but some time
0
.5
3
60
was necessary for equilibration. The electronic absorp-
tion spectrum of a mixture of (Cl)MnOEtPor and
Py C in toluene showed gradual decrease of the
0.4
3
60
absorption intensity at λmax 473 nm and increase of the
0
0
0
.3
.2
.1
Effective rate constants kef of the reaction of (Cl)MnOEtPor
3
with Py C60 in toluene at 298 K
2
Py 60 concentration,
3
C
5
–1
k ×10 ,
L mol
–5
k
ef×10 , s
–1 –1
1
0 M
s
0
4.92
9.84
2.80
5.70
0.59±0.06
1.15±0.12
1.34±0.11
1.70±0.11
4.04
0
4.23
3.91
4.13
4
30
460
490
λ, nm
1
1
Fig. 4. Variation of the electronic absorption spectrum of
(
1
Cl)MnOEtPor in toluene containing Py
0 M) over 5 days.
3
C
60 (c = 4.92×
–
5
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 10 2016

1
506
OVCHENKOVA et al.
0 τ
log(c /c )
log(cPy3C60
)
–4.2
–4.0
–3.8
2
3 60
0
0
0
0
.8
.6
.4
.2
1
–4.8
–4.9
–
–
–
5.0
5.1
5.2
logkef
3
Fig. 6. Logarithmic dependence of kef on the Py C60 concen-
1
00000
200000
τ, s
Fig. 5. Plot of ln(c
(
0
/c
τ
) versus time τ for the reaction of
60 in toluene. Concentration of
Cl)MnOEtPor with Py
3
C
tration for the reaction of (Cl)MnOEtPor with Py
3
C
60 in
–
5
–5
2
2
Py
3
C
60, M: (1) 4.92×10 , (2) 9.84×10 ; R = 0.97‒0.99.
toluene; tanα = 0.89 (R = 0.99).
(
Cl)(Py C )MnOEtPor whose structure is shown
previously, and their structures were optimized by
quantum chemical methods [23, 24].
3
60
below. Such supramolecules are often called coordina-
tion dyads [22]. Analogous indium(III) porphyrin–
fullerene coordination dyads were reported by us
N
N
1
2
N
N
Et
N
Et
Et
Et
N
Mn
N
Et
N
Et
Et
Cl
Et
(
Cl)(Py C60)MnOEtPor
3
The IR spectrum of (Cl)(Py C )MnOEtPor in KBr
3
60
(
Fig. 7) displayed new bands at 1587, 1572, 1452,
1
8
5
427, 1413, 1376, 1185, 1121, 1096, 1063, 1026, 876,
23, 800, 766, 711, 672, 628, 599, 574, 549, and
–
1
27 cm due to N-coordinated Py C ; these bands are
3
60
lacking in the spectrum of (Cl)MnOEtPor. The bands
–
1
at 1427, 1185, 574, and 527 cm correspond to skele-
tal vibrations of C60 [25], and their position almost
does not change in going from free Py C to the dyad.
3
60
Vibrational frequencies typical of the pyridine and
pyrrolidine rings of pure Py C increased by about 5–
3
60
–
1
3
5 cm (see Experimental). A new weak absorption
band at 466 cm is likely to belong to Mn‒NPy
–
1
–1
2
000
1500
1000
ν, cm
stretchings [19].
We previously studied the reaction of Py C with
(acetoxo)[oktakis(4-tert-butylphenyl)tetraazaporphyri-
Fig. 7. IR spectra (KBr) of (1) (Cl)MnOEtPor and
2) (Cl)(Py 60)MnOEtPor. Dotted lines correspond to the
vibrational frequencies of N-coordinated Py
(
3
C
3
60
3
C
60
.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 10 2016

SYNTHESIS AND PROPERTIES OF A NEW (OCTAETHYLPORPHYRINATO)...
1507
nato]manganese(III) (AcO)MnTAP(4-t-BuPh) in tolu-
728 (γ C ‒C). Mass spectrum (MALDI-TOF):
8
β
+
ene [21], which afforded the corresponding coordina-
tion dyad, as in the reaction with (Cl)MnOEtPor.
m/z 587.43 [MnOEtPor] . C H MnN . Calculated:
3
6
44
4
M 587.72.
′-(Pyridin-4-yl)-5′-(pyridin-2-yl)-1′-(pyridin-
-ylmethyl)-2′,5′-dihydro-1′H-pyrrolo[3′,4′:1,9]-
C -I )[5,6]fullerene (Py C ) was synthesized from
–8
However, the reaction rate [k = (2.5 ± 0.26)×10 L×
2
–
1 –1
mol s ) was inversely proportional to the Py C
3
60
3
concentration, and the rate-determining step was
irreversible elimination of acetate ion from
(
6
0
h
3
60
1
C60 and the corresponding azomethine ylide [27] in
,2-dichlorobenzene. Electronic absorption spectrum
toluene), λmax, nm (logε): 294, 313, 433 (3.82). IR
(
AcO)(Py C )–MnTAP(4-t-BuC H ) . Thus, modifica-
3 60 6 4 8
1
(
tion of tetrapyrrole macrocycle via aza or alkyl
substitution sharply (by 6 orders of magnitude) slows
down the formation of porphyrin–fullerene dyad and
changes its composition. Our results may be used for
optimization of the synthesis of porphyrin–fullerene
dyads.
–1
spectrum (KBr), ν, cm : 1721, 1689, 1636, 1587,
1
1
9
5
572, 1455, 1426, 1377, 1356, 1307, 1279, 1231,
215, 1187, 1157, 1123, 1096, 1064, 1048, 1026, 996,
62, 876, 845, 824, 799, 748, 711, 672, 627, 599, 574,
48, 527, 481, 399.
In summary, we have performed a quantitative
study of the formation of coordination dyads from
Pyridine of analytical grade was dried for 48 h over
KOH pellets and distilled (bp 115.3°C). Toluene was
dried over potassium hydroxide and distilled prior to
use (bp 110.6°C). Water content was determined by
Karl Fisher titration; it did not exceed 0.01%.
The reaction of (Cl)MnOEtPor with pyridine in tol-
uene was studied by spectrophotometry at 298–318 K.
(
chloro)(2,3,7,8,12,13,17,18-octaethylporphyrinato)-
manganese(III) and organic bases, pyridine and pyri-
dine-containing fullerene. The reaction kinetics in
toluene were studied by spectrophotometry at 298 K.
The reactants and products were identified by UV-Vis,
IR, and mass spectra, and their structure was optimized
by PM3 quantum-chemical calculations. Taking into
account growing interest in new biologically active
supramolecular systems based on macroheterocycles,
the obtained results are promising for biomedical
studies.
A series of solutions with a constant concentration of
–5
(
Cl)MnOEtPor (10 M) and different concentrations
of pyridine (0–7 M) were prepared. The equilibrium
constant K was determined by Eq. (2) for a three-
component system with two colored components; the
data were processed by the least-squares method im-
plemented in Microsoft Excel.
EXPERIMENTAL
Ai − A
0
The electronic absorption spectra were measured on
an Agilent 8453 spectrophotometer. The IR spectra
were recorded on a Bruker Vertex 80v spectrometer.
The mass spectra were obtained on a Bruker Autoflex
instrument.
A
− A
1
∞
0
K =
⋅
.
(2)
n
Ai − A0
A∞ − A0

Ai − A
0

1
−
0


cPy − c
(Cl)MnOEtPor



A∞ − A
0

(
Chloro)(2,3,7,8,12,13,17,18-octaethylporphyri-
0
Here, cPy and c
are the initial concentra-
(Cl)MnOEtPor
nato)manganese(III) [(Cl)MnOEtPor] was synthe-
sized by reaction of manganese(II) chloride tetra-
hydrate MnCl ·4H O) with 2,3,7,8,12,13,17,18-octa-
tions of pyridine and (Cl)MnOEtPor, respectively, and
A , A , and A are the optical densities at λ 360 nm of
Cl)MnOEtPor, equilibrium mixture at a definite pyri-
0
i
∞
2
2
(
ethylporphyrin in boiling dimethylformamide. The
reaction mixture was diluted with an equal volume of
water and extracted with chloroform. The extract was
repeatedly washed with water to remove excess man-
ganese salt and DMF. The product was identified and
checked for purity by electronic and IR spectroscopy.
Electronic absorption spectrum (toluene), λmax, nm
dine concentration, and product, respectively. The
relative error in the determination of K did not exceed
1
5%. The stoichiometric coefficient n was determined
as the slope of the straight line logI = f(logc ), where
i
Py
I
i
= (A
i
– A )/(A
0 ∞
i
– A ).
(
5
logε): 359 (4.94), 428 (4.15), 473 (4.76), 562 (4.00),
The kinetics of the reaction of (Cl)MnOEtPor with
Py C in toluene were studied by spectrophotometry
91 (3.71), 677 (3.21), 770 (3.33). IR spectrum (KBr),
3
60
–
1
ν, cm : 2966, 2872 (CH ); 2931 (CH ); 1632, 1604
3
2
under pseudofirst-order conditions at 298 K (Py C
3 60
–4
(C=C, C=N; 1480, 1464, 1451, 1373 (δCH , δCH );
3 2
concentration 0–1.5×10 M). The upper limit of the
1
315 (C‒N); 1272, 1148, 1112, 1062, 1019, 989, 962
1
(macrocycle); 1055 (δC ‒C); 841 (γCmeso‒H); 749,
Provided by Prof. P.A. Troshin.
β
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 10 2016

1
508
OVCHENKOVA et al.
Py C concentration was determined by its solubility
10. Huang, L., Dai, T., and Hamblin, M., Meth. Mol. Biol.,
010, vol. 635, p. 155.
1. Meloa, W., Leeb, A.N., Perussi, J.R., and Hamblin, M.R.,
3
60
2
in toluene. Solutions of (Cl)MnOEtPor and Py C in
3
60
1
freshly distilled toluene were prepared just before use
to avoid peroxide formation. The optical densities of
a series of solutions with a constant concentration of
Photodiagn. Photodyn. Ther., 2013, vol. 10, p. 647.
1
1
1
2. Lopes, M., Alves, C.T., Raju, B.R., Gonçalves, M.S.T.,
Coutinho, P.J.G., Henriques, M., and Belo, I., J. Photo-
chem. Photobiol., B, 2014, vol. 141, p. 93.
3. Dukhande, V.V., Malthankar-Phatak, G.H., Hugus, J.J.,
Daniels, C.K., and Lai, J.C.K., Neurochem. Res., 2006,
vol. 31, p. 1349.
4. Xiang-Jiao, X., Zhi, X., Zu-De, Q., An-Xin, H., Chao-
Hong, L., and Yi, L., Thermochim. Acta, 2008, vol. 476,
p. 33.
–
5
(
Cl)MnOEtPor (1.0×10 M) and different Py C con-
3 60
centrations were measured at λ 475 nm immediately
after mixing the reactants and after a time. The spectra
were recorded relative to a solution of Py C with the
3
60
same concentration. Solutions were maintained at
98±0.1 K in closed quartz cells. The rate constants
for the reaction of (Cl)MnOEtPor with Py C were cal-
2
3
60
culated assuming first-order kinetics (excess Py C ):
3
60
1
1
1
5. Karimipour, G., Kowkabi, S., and Naghiha, A., Braz.
Arch. Biol. Technol., 2015, vol. 58, p. 431.
6. Spesia, B., Milanesio, M.E., and Durantini, E.N., Eur. J.
Med. Chem., 2008, vol. 43, p. 853.
7. Fedorova, E., Klimova, R.R., Tulenev, Yu.A., Chi-
chev, E.V., Kornev, A.B., Troshin, P.A., and
Kushch, A.A., Mendeleev Commun., 2012, vol. 22,
p. 254.
k
ef = 1/τln[(A
0
∞ τ ∞
– A )/(A – A )].
Here, A , A , and A are the optical densities of the
0
τ
∞
reaction mixture at a working wavelength at the initial
moment, after time τ, and after reaction completion.
Quantum chemical calculations (PM3) [28–30] of
isolated (Cl)MnOEtPor molecule and its complex with
pyridine were performed with full geometry optimiza-
18. Zaitseva, S.V., Zdanovich, S.A., and Koifman, O.I.,
Russ. J. Gen. Chem., 2013, vol. 83, p. 738.
19. Klyueva, M.E., Doctoral (Chem.) Dissertation,
Ivanovo, 2006.
–
1
–1
tion until a gradient of 0.001 kJ mol Å . The
averaged bond lengths and bond angles given in [31]
were used as initial geometric parameters.
20. Vinogradskii, A.G. and Sidorov, A.N., Koord. Khim.,
1
979, vol. 5, p. 800.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 15-43-03013-r-tsentr-a) using the facilities of the
Upper Volga Joint Regional Center for Physico-
chemical Studies.
2
2
1. Ovchenkova, E.N., Bichan, N.G., and Lomova, T.N.,
Tetrahedron, 2015, vol. 71, p. 6659.
2. Razumov, V.F., Abalyaeva, V.V., and Efimov, O.N.,
Nanostrukturirovannye materialy dlya zapasaniya i pre-
obrazovaniya energii (Nanostructured Materials for
Energy Storage and Conversion). Ivanovo: Ivanov. Gos.
Univ., 2009.
REFERENCES
2
3. Lomova, T.N., Malov, M.E., Klyuev, M.V., and Tro-
1
2
. Overbye, K.M. and Barrett, J.F., Drug Discovery Today,
005, vol. 10, p. 45.
. Levy, S.B., Adv. Drug. Delivery Rev., 2005, vol. 57,
shin, P.A., Macroheterocycles, 2009, vol. 2, p. 164.
2
2
4. Lomova, T.N., Malov, M.E., Klyuev, M.V., and Tro-
shin, P.A., Advances in Materials Science Research,
Wythers, M.C., Ed., New York: Nova Science, 2011,
vol. 2, p. 143.
p. 1446.
3
4
5
. Alanis, A.J., Arch. Med. Res., 2005, vol. 36, p. 697.
. Chopra, I., Curr. Opin. Microbiol., 1998, vol. 1, p. 495.
. Spellberg, B., Powers, J.H., Brass, E.P., Miller, L.G., and
25. Eletskii, A.V. and Smirnov, B.M., Phys.–Usp., 1993,
vol. 36, p. 202.
Edwards, J.E., Clin. Infect. Dis., 2004, vol. 38, p. 1279.
26. Adler, A.D., Longo, F.R., Kampus, F., and Kim, J.,
6
7
. Livermore, D.M., Lancet Infect. Dis., 2005, vol. 5,
p. 450.
. Tome, J.P., Neves, M.G., Tome, A.C., Cavaleiro, J.A.,
Soncin, M., Magaraggia, M., Ferro, S., and Jori, G.,
J. Med. Chem., 2004, vol. 47, p. 6649.
J. Inorg. Nucl. Chem., 1970, vol. 32, p. 2443.
27. Troshin, P.A., Troyanov, S.I., Boiko, G.N., Lyubov-
skaya, R.N., Lapshin, A.N., and Goldshleger, N.F.,
Fullerenes, Nanotubes, Carbon Nanostruct., 2004,
vol. 12, p. 435.
2
8. Stewart, J.J.P., J. Comput. Chem., 1989, vol. 10, p. 209.
8
9
. Branland, V.S.P., Chaleix, V., Granet, R., Guilloton, M.,
Lamarche, F., Verneuil, B., and Krausz, P., Bioorg. Med.
Chem. Lett., 2004, vol. 14, p. 4207.
. Banfi, S., Caruso, E., Buccafurni, L., Battini, V.,
Zazzaron, S., Barbieri, P., and Orlandi, V., J. Photo-
chem. Photobiol., B, 2006, vol. 85, p. 28.
29. Stewart, J.J.P., J. Comput. Chem., 1989, vol. 10, p. 221.
30. Stewart, J.J.P., J. Comput.-Aided Mol. Des., 1990,
vol. 4, p. 1.
31. Lomova, T.N. and Berezin, B.D., Russ. J. Coord.
Chem., 2001, vol. 27, p. 85.
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