ISSN 1063-7850, Technical Physics Letters, 2013, Vol. 39, No. 7, pp. 664–668. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © G.M. Mikheev, I.P. Angelov, V.N. Mantareva, T.N. Mogileva, K.G. Mikheev, 2013, published in Pis’ma v Zhurnal Tekhnicheskoi Fiziki, 2013, Vol. 39,
No. 14, pp. 86–94.
664
The interest in the optical and nonlinear optical
properties of dye compounds based on phthalocyanine
(Pc) is due to their applicability in medicine for pho-
todynamic therapy and diagnostics of cancer tumors,
as well as in the technology of gas sensors, solar batter-
ies, thin-film electronic devices, light-emitting
diodes, photovoltaic devices, optical limiting (OL)
devices, etc. [1–4]. The flexible chemical structure of
phthalocyanine makes it possible to attach various
functional groups and radicals (as well as various
atoms coordinating phthalocyanine macrocycle) to it.
As a result, one can design various metal nanocom-
plexes with different optical and nonlinear optical
properties based on phthalocyanine.
There are many publications devoted to the optical
and nonlinear optical properties of solutions and film
structures of Pc compounds with various metals and
radicals (see, for example, [5–11]). From the point of
view of photodynamic therapy, ZnPc compounds,
which are characterized by high output of singlet oxy-
gen upon photoexcitation [12], are most interesting.
However, ZnPc has insufficient selectivity of “attach-
ing” to the tumor cells. To overcome this drawback,
radicals are attached to ZnPc molecules in order to
improve their selective properties and increase their
ability to be accumulated on pathological cells, taking
into account the metabolism of pathogens [13].
Galactopyranosyl can play the role of such a radical. It
is noteworthy that radical Gal can be located in both
peripheral (p-GalZnPc) and nonperipheral (n-
GalZnPc) positions with respect to the ZnPc macro-
cycle (Fig. 1) [14]. Recently, ZnPc dyes with galacto-
pyranosyl radicals were synthesized in [15, 16]. Study
of their physical, physicochemical, and biochemical
properties showed that they depend strongly on the
position of the Gal radical in the dye chemical struc-
ture. Due to these features, the aforementioned dyes
can be used as a functional component of nanocom-
plexes designed for theranostics [3]. One must know
the optical and nonlinear optical properties of these
newly synthesized compounds to use them as diagnos-
tic markers. However, to the best of our knowledge,
the nonlinear properties (in particular, OL) in solu-
tions of these compounds have not been investigated.
The purpose of our study is to fill in this gap.
The objects of study, p-GalZnPc and n-GaLZnPc
dyes with a chemical formula C
80
H
88
N
8
O
24
Zn, were
synthesized as a result of the interaction of ZnPc
(C
32
H
16
N
8
Zn) with D-galactopyranose (C
12
H
20
O
6
)
in dry argon by the technique described in [14–16].
The thus-prepared compounds were identified
and characterized on an NMR spectrometer
(AVANCE AV600 II+ NMR), which recorded spectra
of
1
H nuclei at a frequency of 600 MHz; an electron-
ionization mass spectrometer (Bruker Esquire LC);
and an IR spectrometer (BIORAD SPC-3200 FTS7
FT-IR). The diameter of disklike conjugants p-
GalZnPc and n-GalZnPc, calculated based on the
data of [17], is in the range from 2 to 2.5 nm.
Thresholds of Optical Limiting in Solutions
of Nanoscale Compounds of Zinc Phthalocyanine
with Galactopyranosyl Radicals
G. M. Mikheev, I. P. Angelov, V. N. Mantareva, T. N. Mogileva, and K. G. Mikheev
Institute of Mechanics, Ural Branch, Russian Academy of Sciences, Izhevsk, Russia
Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria
e-mail: mikheev@udman.ru
Received March 14, 2013
Abstract—The optical limiting (OL) of nanosecond laser pulses in solutions of newly synthesized dyes in
dimethyl sulfoxide (DMSO) has been investigated. These dyes are compounds of zinc phthalocyanine (ZnPc)
with D-galactopyranosyl radicals (Gal) located in the peripheral (p-GalZnPc) and nonperipheral (n-
GalZnPc) positions with respect to the ZnPc macrocycle. Experiments have been performed using laser radi-
ation with a wavelength of 532 nm, at which the optical absorbance of solutions of ZnPc, p-GalZnPc and n-
GalZnPc dyes is four orders of magnitude lower than the absorbance in the peaks at wavelengths of 671, 680,
and 701 nm, respectively. It is established that solutions of p-GalZnPc and n-GalZnPc in DMSO have a much
lower OL threshold in comparison with ZnPc solution; the nonlinearity of p-GalZnPc solutions exceeds that
of n-GalZnPc solutions. OL thresholds for the dyes under study in a wide concentration range are deter-
mined.
DOI: 10.1134/S1063785013070195