ISSN 10274510, Journal of Surface Investigation. Xray, Synchrotron and Neutron Techniques, 2013, Vol. 7, No. 6, pp. 1133–1136. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © A.A. Kaznacheevskaya, O.A. Kizima, L.A. Bulavin, A.V. Tomchuk, V.M. Garamus, M.V. Avdeev, 2013, published in Poverkhnost’. Rentgenovskie,
Sinkhrotronnye i Neitronnye Issledovaniya, 2013, No. 12, pp. 21–24.
1133
INTRODUCTION
Currently, cluster formation in fullerene solutions
is a topical issue in colloidal chemistry [1]. The study
of fullerene solutions is important from both funda
mental (information about the cluster state of matter)
and practical points of view. The applied interest in
fullerene solutions is caused, in particular, by the bio
activity of fullerenes; hence, it is necessary to search
for watersoluble and stable forms of these highsym
metry molecules. Despite the large number of experi
mental and theoretical studies on this subject [2, 3],
the nature of cluster formation, cluster structure, and
the anomalous properties of fullerene solutions caused
by the presence of clusters are still far from being com
pletely understood. The purpose of our study is to clar
ify this question.
It was previously shown that the transition from a
molecular solution to a cluster one occurs with time in
the С
60
/Nmethylpyrrolidone (NMP) system [4]. One
can state that an overwhelming number of the initially
dissolved С
60
molecules finally aggregate into clusters
(up to 500 nm in size), which remain stable for a long
(at least, 1 yr) time. This system also exhibits an inter
esting effect of cluster reorganization after adding
some water [5, 6]: С
60
/NMP complexes are partially
dissolved in the NMP/H
2
O mixture [7]. This effect
depends on the age of the initial solution [6].
The reorganization of the cluster state (specifically,
a significant decrease in the characteristic size of clus
ters) can easily be detected by smallangle neutron
scattering (SANS) [5, 6]. Concerning dynamic light
scattering (DLS), which is used to record clusters in
the final (cluster) С
60
/NMP solution, it was only
reported that the characteristic size of the clusters
tends to decrease after dilution of this system with
water. We analyzed the change in the DLS spectra after
adding water to С
60
/NMP based on quantitative
reconstruction of the sizedistribution function of the
clusters. To obtain a more pronounced DLS effect,
water is added to a relatively fresh (two week old) ini
tial solution. The data obtained are compared with the
previous SANS results for rather old (more than one
month) initial С
60
/NMP solutions. The purpose of
this study was to reveal the degree of agreement
between the data on the size characteristics of polydis
perse clusters obtained by two different methods.
EXPERIMENTAL
To prepare the С
60
/NMP system, a fullerene of
purity grade >99.5% (Fullerenovie Tekhnologii) was
dissolved in NMP of purity grade >99.5% (Merck) and
stirred for four days at room temperature. The concen
tration (0.89 mg/mL) was determined from the
adsorption coefficient in the UV–visible spectrum
Reorganization of the Cluster State
in a C
60
/NMethylpyrrolidone/Water Solution:
Comparative Characteristics of Dynamic Light Scattering
and SmallAngle Neutron Scattering Data
A. A. Kaznacheevskaya
a, b
, O. A. Kizima
a, c
, L. A. Bulavin
c
, A. V. Tomchuk
a, c
,
V. M. Garamus
d
, and M. V. Avdeev
a
a
Frank Laboratory of Neutron Physics, Joint Institute for Nuclear Research, Dubna, 141980 Russia
b
Tula State University, Tula, 300012 Russia
c
Shevchenko National University, Kyiv, 03022 Ukraine
d
HelmholtzZentrum Geesthacht, 21502 Geesthacht, Germany
Received February 11, 2013
Abstract—Data on dynamic light scattering from cluster solutions of C
60
fullerenes in Nmethylpyrrolidone
(NMP) and its mixture with water are analyzed. Initial C
60
/NMP solutions kept for two weeks (i.e., fresher
than those analyzed previously) are considered, where the effect of clusterstate reorganization after adding
water is recorded more reliably. Based on the sizedistribution functions of the clusters, obtained from
dynamic light scattering data, model curves of smallangle neutron scattering are calculated and compared
with the experimental data.
DOI: 10.1134/S102745101306030X