Synthesis and Antimicrobial Activity of a Pyridine Complex of (Acetato)[5,10,15,20-tetrakis(N-methylpyridin- 4-yl)porphinato]manganese(III) Tetratosylate

Article abstract of DOI:10.1134/S1070363218080170

Aiming at preparation of new biologically active donor?acceptor complexes, a water-soluble manganese(III) complex with 5,10,15,20-tetrakis(N-methylpyridin-4-yl)porphine tetratosylate was synthesized and its reaction with pyridine was studied by spectrophotometry using the molar ratio method. In water a 1: 1 donor?acceptor complex with pyridine is formed. The chemical structure of the compounds was established by spectral methods. (Acetato)[5,10,15,20-tetrakis(N-methylpyridin-4-yl)porphinato]manganese(III) tetratosylate and especially its donor?acceptor complex with pyridine showed an antifungal activity against Candida albicans.

Full text of DOI:10.1134/S1070363218080170

ISSN 1070-3632, Russian Journal of General Chemistry, 2018, Vol. 88, No. 8, pp. 1657–1662. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © E.N. Ovchenkova, N.G. Bichan, A.V. Lyubimtsev, E.V. Garasko, T.N. Lomova, 2018, published in Zhurnal Obshchei Khimii, 2018,
Vol. 88, No. 8, pp. 1337–1342.
Synthesis and Antimicrobial Activity of a Pyridine Complex
of (Acetato)[5,10,15,20-tetrakis(N-methylpyridin-
4-yl)porphinato]manganese(III) Tetratosylate
E. N. Ovchenkovaa*, N. G. Bichana, A. V. Lyubimtsevb, E. V. Garaskoc, and T. N. Lomovaa
a G.A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, ul. Akademicheskaya 1, Ivanovo, 153045 Russia
*e-mail: enk@isc-ras.ru
b Ivanovo State University of Chemistry and Technology, Ivanovo, Russia
c Ivanovo State Medical Academy, Ministry of Health of the Russian Federation, Ivanovo, Russia
Received April 5, 2018
Abstract—Aiming at preparation of new biologically active donor‒acceptor complexes, a water-soluble
manganese(III) complex with 5,10,15,20-tetrakis(N-methylpyridin-4-yl)porphine tetratosylate was synthesized
and its reaction with pyridine was studied by spectrophotometry using the molar ratio method. In water a 1 : 1
donor‒acceptor complex with pyridine is formed. The chemical structure of the compounds was established by
spectral methods. (Acetato)[5,10,15,20-tetrakis(N-methylpyridin-4-yl)porphinato]manganese(III) tetratosylate
and especially its donor‒acceptor complex with pyridine showed an antifungal activity against Candida albicans.
Keywords: water-soluble manganese(III) porphyrin, pyridine, donor‒acceptor complex, spectral properties,
antimicrobial and antifungal activity
DOI: 10.1134/S1070363218080170
The problem of resistance of common bacteria,
fungi, and pathogenic microorganisms raises demand
for new antibacterial and antifungal agents. Anti-
microbial photodynamic therapy is one of the modern
methods of microbial infections treatment [1–3].
Among antibacterial and antifungal agents porphyrin
complexes attract attention [4–6] owing to their ability
to act as photosensitizers. Some porphyrins and related
compounds were found to exhibit phototoxicity to
bacteria and fungi [7–10]. Porphyrins and metal por-
phyrins bearing a positive charge are excellent photo-
sensitizers for photodynamic inactivation of micro-
organisms, in particular, Escherichia coli [11–13]. It
was found that the efficiency of such photosensitizers
depends on their ability for generation of singlet
oxygen and tendency for aggregation, as well as on the
distribution of charge in the molecule and amphi-
philicity.
are close to natural systems, where different photo-
and redox-active components are held together by
noncovalent interactions (hydrogen bond, π–π inter-
action, metal‒ligand axial coordination). The sug-
gested method of modifying compounds is relatively
facile in implementation and presumes varying their
properties.
As the object for study we chose a cationic complex
of manganese with porphyrin due both to biological
activity of compounds of this metal and use them as
antibacterial agents in antimicrobial photodynamic
therapy. Manganese(III) porphyrins are much more
potent antibacterial and antifungal agents than free
porphyrins [14]. Cationic manganese(III) pyridinyl-
porphyrins with substituents on the pyridine N atoms
have a high therapeutic potential as radio- and
chemosensitizers in cancer therapy [15–18]. The
antibacterial activity of ebselen(tetraphenylporphyrinato)-
manganese(II) conjugate (where ebselen is 2-phenyl-
1,2-benzoselenazol-3-one) [19] is several times higher
compared to (tetraphenylporphyrinato-manganese(II).
As a approach to obtain new antibacterial agents we
suggested
a
donor‒acceptor assembly to form
additional centers of biological activity in the mole-
cule. Design of supramolecular noncovalent com-
plexes attracts researchers’ attention, because they just
Taking the above into account we synthesized a
complex of manganese(III) acetate with 5,10,15,20-
1657

1658
OVCHENKOVA et al.
Scheme 1.
CH3
N
4+
O_
S
O
O
OAc
N
N
4
Mn
N
H3C
N CH3
N
NH
CH3
N
CH3
(AcO)MnTMPyP
tetrakis(N-methylpyridin-4-yl)porphine
(Н2TMPyP)
the synthesized complex of manganese(III) with
5,10,15,20-tetrakis(N-methylpyridin-4-yl)porphine tetra-
tosylate were confirmed by the electron absorption, IR,
tetratosylate (AcO)MnTMPyP (Scheme 1) and used
this complex to synthesize a donor‒acceptor system
with the biologically active base pyridine (Py).
1
and Н NMR spectroscopy. The electron absorption
spectrum (ESP) corresponds to the compound
(AcO)MnIIIP. The spectrum of (AcO)MnTMPyP in
water shows a band at 463 nm (Q-band), which is
absent from the spectra of Mn(II), Mn(IV), and Mn(V)
compounds [24–26]. The nature of the acido ligand
corresponds to the anionic composition of the starting
salt and is confirmed by the IR spectral data.
The choice of organic base was motivated by the
fact that the pyridine molecule possesses π-acceptor
properties and is readily accommodated together with
the porphyrin macrocycle in a single coordination shell
of a metal cation [20, 21]. Moreover, pyridine is the
structural fragment of a number of biologically active
compounds: vitamins, antibiotics, and alkaloids.
The reaction of the (AcO)MnTMPyP complex with
pyridine in water was studied over a wide con-
centration range of the latter. Pyridine is added to the
aqueous solution of (AcO)MnTMPyP, the band at
463 nm in the ESP of the complex gradually decreases,
and the band at 422 nm shifts red by 8 nm (see the
figure). The spectrophotometric titration curve looks
like a straight line with a bend at the lowest optical
density of the solution. The ESP of the reaction
product does not change with time and is characteristic
of a Mn(III)-coordinated macrocyclic chromophore.
The figure and the experimentally established reverse-
bility of spectral changes with dilution of the solution
provide evidence that the reaction of (AcO)MnTMPyP
with pyridine proceeds in one stage until equilibrium (1)
is established; the equilibrium constant K is 2.45±
0.60 L/mol. The slope of the log I–f(log сPy) plot,
which measures the stoichiometry for pyridine, is close
to one (tan α = 0.8).
The Н2TMPyP complex is not associated in
aqueous solutions throughout a wide range of
concentrations and pH [22]. To find out whether we
can neglect association of (AcO)MnTMPyP when
studying its reaction with pyridine in water, we
checked the validity of the Bouguer–Lambert–Beer
law for freshly prepared and stored aqueous solutions
of manganese(III) porphyrin in the concentration range
of the spectrophotometric experiment. The resulting
data showed that (AcO)MnTMPyP was present in the
solutions in a nonassociated form and, therefore, the
spectrophotometric data could be analyzed taking into
account the monomeric form of the macrocyclic
compound.
The spectral data obtained in the present work are
identical to those in [23] and reliably characterize the
synthesized
5,10,15,20-tetra(pyridin-4-yl)porphine
(Н2TMPyP). The individuality and spectral purity of
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SYNTHESIS AND ANTIMICROBIAL ACTIVITY OF A PYRIDINE COMPLEX
(a) (b)
1659
А
А
λ, nm
сРу, M
(a) Change of the ESP of a solution of (AcO)MnTMPyP in water (c = 1.2×10–5 M) with addition of pyridine from 0 (initial curve)
to 7.45 M (final curve) and (b) spectrophotometric titration curve at 463 nm.
K
paramagnetic complex [31]. The upfield Hβ signals
(AcO)MnTMPyP + Py ⇄ (AcO)(Py)MnTMPyP.
(1)
(–31.90 ppm) are broadened [31]. The signals of
protons Ho and Hm are observed at 9.18 and 8.68 ppm,
and the НTos signals appear at 7.41 and 7.03 ppm [32].
The peripheral, acetate, and tosylate СН3 protons give
signals at 4.72, 4.26, 2.67, and 2.03 ppm [33]. The
addition of pyridine (at the concentration close to the
equivalence point) to a solution of (AcO)MnTMPyP in
D2О is accompanied by the appearance of two new
signals of pyridine ring protons at 8.99 and 7.74 ppm,
which are slightly shifted downfield (up to 0.5 ppm)
with respect to the signals of an uncoordinated
pyridine [34]. The formation of the Py→Mn donor‒
acceptor bond shifts the macrocycle signals. The Ho,
The reaction product involves a donor‒acceptor
interaction between manganese(III) porphyrine and
pyridine. The nature of the interaction is confirmed by
spectral data (see the figure) indicative of an axial
addition of the pyridine molecule without elimination
of the acetate ion. Such boding reduces the deviation
of the central Mn atom from the N4 plane of the
starting porphyrin and shifts bands in the ESP. The
observed spectral changes are consistent with
published data [27]. Further evidence for the NPy→Mn
1
donor‒acceptor bonding was obtained by IR and Н
NMR spectroscopy.
1
Hm, and НTos signals in the H NMR spectrum of the
The IR spectrum of (AcO)(Py)MnTMPyP is
characterized by slight changes in the positions and
intensities of some bands of the porphyrin macrocycle.
The bands of the axial acetate group, whose position
allows for the judgement on the nature of АсО–
binding in the pyridine complex, too, are slightly
shifted. In the IR spectrum of (AcO)(Py)MnTMPyP,
the νas(O–C–O) and νs(O–C–O) bands of the АсО–
ligand are observed at 1641 and 1384 cm–1,
respectively. The difference in the wave numbers of
these two bands is 257 cm–1 and suggests a bidentate
covalent binding of the acetate ion [28, 29], like in the
starting complex. The new weak signal at 468 cm–1 is
assignable to the Mn–NPy bond [30].
(AcO)(Py)MnTMPyP complex shift downfield by 0.03–
0.09 ppm, whereas the Hβ signals shift upfield to
–32.45 ppm. Such a large upfield shift of the β-proton
signals is associated with the change in the orbital
symmetry of manganese and the deformation of the
porphyrin macrocycle upon the axial coordination of
the ligand [31].
Testing of antibacterial and antifungal activity of
the synthesized manganese(III) complex was per-
formed using as test objects gram-positive (Staphylo-
coccus aureus) and gram-negative bacteria (Escherichia
coli) and yeast-like fungi (Candida albicans) in solid
and liquid growth media. The results of testing of
fabric samples on a solid growth medium (bacterial
and fungal counts after 24 h incubation of Petri dishes
The 1Н NMR spectrum of (AcO)MnTMPyP, where
the configuration of the central atom is 3d4, suggests a
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 8 2018

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OVCHENKOVA et al.
in a thermostat at 37°С) gave too-numerous-to-count
results (TNTC), specifically 1000 CFU/mL, with all
test cultures.
and 5 mL of concentrated ammonia were added to the
residue. The precipitate was filtered off, washed with
methanol, and dried. The reaction product was
extracted in a Soxhlet apparatus with chloroform, and
the obtained solution was subjected to chromatography
on alumina (Brockmann activity grade II). The eluate
was reduced to a minimal volume (until precipitate
formation) and the reaction product was precipitated
with methanol, filtered off, washed with methanol, and
dried at 60°С in a vacuum. The residue in the thimble
of the Soxhlet apparatus was dissolved in 140 mL of
3% HCl, 4–5 mL of concentrated ammonia and the
precipitate was filtered off, washed with water, and
dried at 60°С in a vacuum. Yield 1.2 g (27%). ESP
(CHCl3), λmax, nm (log ε): 417 (5.62), 514 (4.30), 546
The results of testing in liquid growth media with
the subsequent inoculation provided evidence for the
results obtained in solid growth media (TNTC, 1000
KОЕ/mL) with Escherichia coli and Staphylococcus
aureus. The highest antifungal activity of the donor‒
acceptor complex of manganese(III)porphyrine with
pyridine was shown against Candida albicans fungi in
liquid growth media with (365 nm) and without
preliminary UV irradiation and subsequent inoculation.
The (AcO)MnTMPyP complex has a weak antifungal
effect. The testing results provide evidence for the
expected synergistic effect of the combination of the
components of the (AcO)MnTMPyP–Py donor‒acceptor
system.
1
(3.79), 589 (3.82), 643 (3.43). Н NMR spectrum
(CDCl3), δ, ppm: 9.08 d (8H, H2,6Py), 8.87 s (8H, Hβ),
8.18 d (8H, H3,5Py), –2.92 s (2H, NH).
Silver and copper complexes of 5,10,15,20-tetrakis-
(N-methylpyridin-4-yl)porphine tetratosylate showed
activity against Staphylococcus aureus, Escherichia
coli, and Candida albicans in solid or liquid growth
media [35]. The highest activity against all the
mentioned test cultures was found to be characteristic
of AgTMPyP, while CuTMPyP was inactive against
Candida albicans.
(Acetato)[5,10,15,20-tetra(pyridin-4-yl)porphinato]-
manganese(III). 0.5 g (0.8 mmol) of 5,10,15,20-tetra-
(pyridin-4-yl)porphine and 1.9 g (6.8 mmol) of
Mn(OAc)2·6H2O was refluxed for 2 h in 100 mL of
DMF. The reaction mixture was cooled down to room
temperature and poured into water. The precipitate was
filtered off, dried in a vacuum at 60°С and purified by
column chromatography on alumina (Brockmann
activity grade II). The eluate was evaporated to dryness.
Yield 0.4 g (74%). Mass spectrum (MALDI‒TOF),
m/z: 671.22 [M – AcO]+. С40H24MnN8. Мcalc 671.00.
Thus, the antimicrobial activity depends both on the
nature and coordination saturation of the central metal
atom and on the presence or absence of additional
centers of biological activity. The results obtained in
the present work contribute to the theoretical concepts
of the coordination chemistry of macroheterocyclic
compounds and create prerequisites for the develop-
ment of antibacterial and antifungal agents.
(Acetato)[5,10,15,20-tetrakis(N-methylpyridin-4-
yl)porphinato]manganese(III) tetratosylate (AcO)
MnTMPyP. A solution of 0.1 g (0.16 mmol) of
(acetato)[5,10,15,20-tetra(pyridin-4-yl)porphinato]-
manganese(III) and 1.0 g (5.4 mmol) of methyl
p-toluenesulfonate was refluxed for 1 h in 5.0 mL of
anhydrous DMF. The reaction mixture was cooled
down and diluted with 5.0 mL of benzene and the
precipitate was filtered off, washed with benzene, and
dried in a vacuum at 60°С. Yield 0.18 g (82.5%). IR
spectrum (KBr), ν, cm–1: 373, 399, 446, 494, 533, 571,
689, 711, 813, 846, 868, 890, 902, 970, 1013, 1038,
1128, 1189, 1278, 1323, 1346, 1381 [νs(O–C–O)],
1396, 1463, 1496, 1509, 1540, 1561, 1599, 1642
[νas(O–C–O)]. ESP (Н2О), λmax, nm (log ε): 379 sh,
EXPERIMENTAL
The ESP were recorded on an Agilent 8453
spectrophotometer. The IR spectra were obtained on a
1
VERTEX 80v spectrometer. The Н NMR spectra
were run on a Bruker Avance III-500 spectrometer.
The mass spectra were measured on a Shimadzu
Confidence instrument.
5,10,15,20-Tetra(pyridin-4-yl)porphine was syn-
thesized by the procedure in [23]. A mixture of 2 mL
(0.03 mol) of pyrrole and 2.7 mL (0.03 mol) of
pyridine-4-carbaldehyde were added to 100 mL of a
boiling propionic acid. The resulting mixture was
refluxed for 1.5 h and cooled down. Propionic acid
was distilled off in a vacuum, and 60 mL of methanol
1
422 (4.84), 463 (4.91), 518 (3.83), 559 (3.91). H
NMR spectrum (CDCl3), δ, ppm: 9.18 br.s (Ho), 8.68
br.s (Hm), 7.41 br.s (HoTos), 7.03 br.s (HmTos); 4.72 br.s,
4.26 br.s, 2.67 br.s, 2.03 br.s (CH3), –31.90 br.s (Hβ).
(Acetato)[5,10,15,20-tetrakis(N-methylpyridin-4-
yl)porphinato](pyridine)manganese(III) tetra-
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SYNTHESIS AND ANTIMICROBIAL ACTIVITY OF A PYRIDINE COMPLEX
1661
tosylate (AcO)(Py)MnTMPyP. IR spectrum (KBr), ν,
cm–1: 382, 394, 447, 468 (Mn–NPy), 526, 569, 683,
712, 815, 865, 888, 970, 1012, 1034, 1123, 1191,
1211, 1280, 1345, 1384 [νs(O–C–O)], 1402, 1464,
1496, 1539, 1562, 1599, 1641 [νas(O–C–O)]. ESP
(Н2О), λmax, nm (log ε): 379 sh, 430, 463, 519, 563. 1H
NMR spectrum (CDCl3), δ, ppm: 9.23 br.s (Ho), 8.99
br.s (HPy), 8.77 br.s (Hm), 7.74 br.s (HPy), 7.44 br.s
(HoTos), 7.08 br.s (HmTos); 4.74 br.s, 4.26 br.s, 2.68 br.s,
2.10 br.s (CH3), –32.45 br.s (Hβ).
completely converts into the donor‒acceptor complex
(AcO)(Py)MnTMPyP. The samples 1×1 cm in size
were placed in Petri dishes with the test cultures
Staphylococcus aureus and Escherichia coli and fungi
Candida albicans. The tests were performed in liquid
or solid media both under white or UV light (365 nm)
for 4 min.
ACKNOWLEDGMENTS
The work was financially supported by the Ministry
of Education and Science of the Russian Federation
through state contract [no. 4.1929.2017/4.6, synthesis
of a manganese(III) complex of 5,10,15,20-tetrakis(N-
methylpyridin-4-yl)porphine tetratosylate].
The reaction of (AcO)MnTMPyP with pyridine was
studied by spectrophotometry at 298 K in water using
the molar ratio method. A series of aqueous solutions
with a constant concentration of manganese(III)por-
phyrine (1.2×10–5 M) and varied concentration of
pyridine (0–7.45 M). Before use analytical grade
pyridine was dried for 2 days over KOH granules and
then distilled (bp 115.3°С).
CONFLICT OF INTERESTS
No conflict of interest was declared by the authors.
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