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Surface properties of fullerenol C60(OH)20 solutions

Alexander V. Akentiev, Sofiia B. Gorniaia, Nikolaj A. Isakov,

Vasylij T. Lebedev, Olga Yu. Milyaeva, Victor P. Sedov,
Konstantin N. Semenov, Kirill A. Timoshen, Boris A. Noskov

PII: S0167-7322(20)30254-3
DOI: https://doi.org/10.1016/j.molliq.2020.112904
Reference: MOLLIQ 112904

To appear in: Journal of Molecular Liquids

Received date: 13 January 2020

Revised date: 6 March 2020
Accepted date: 13 March 2020

Please cite this article as: A.V. Akentiev, S.B. Gorniaia, N.A. Isakov, et al., Surface
properties of fullerenol C60(OH)20 solutions, Journal of Molecular Liquids (2020),
https://doi.org/10.1016/j.molliq.2020.112904

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© 2020 Published by Elsevier.

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Surface Properties of Fullerenol C60(OH)20 Solutions

Alexander V. Akentiev,1 Sofiia B. Gorniaia,1 Nikolaj A. Isakov,1 Vasylij T. Lebedev,2 Olga Yu.
Milyaeva1, Victor P. Sedov,2 Konstantin N. Semenov,3 Kirill A. Timoshen,1 Boris A. Noskov1*
1
St. Petersburg State University, 7/9 Universitetskaya nab., St. Petersburg 199034, Russia
2
B.P. Konstantinov Petersburg Nuclear Physics Institute, NRC Kurchatov Institute, 188300
Gatchina, Leningrad, Russia
3
Pavlov First Saint Petersburg State Medical University, L’va Tolstogo str. 6–8, Saint
Petersburg, 197022, Russia

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Keywords: fullerene derivatives, dilational surface rheological properties, surface structure,
adsorption kinetics

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Abstract
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The surface properties of fullerenol C60(OH)20 solutions differ significantly from the
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properties of solutions of more hydrophilic fullerenols. At concentrations below 1 g/l, dynamic
surface elasticity proves to be very high (up to 300 mN/m), while surface tension decreases only
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slightly. The adsorption layer is very sensitive to mechanical perturbations of the solution
surface, and surface elasticity decreases under surface compression. The adsorption layer is
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macroscopically homogeneous but contains microscopic aggregates. The layer can be easily
transferred from the liquid surface onto a solid support.
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*
Corresponding author: e-mail b.noskov@spbu.ru; tel: +78124284093 (B.A. Noskov)
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Introduction
Fullerenes have been used in numerous applications in various fields such as chemistry,
cosmetic industries, optoelectronics, and construction [1–5]. There are also great prospects for
their use in medicine as anticancer and antiviral agents, and as powerful antioxidants as well as
drug and gene delivery vehicles [6–11]. At the same time, their very low solubility in water
(approximately 1.3 × 10-13 g/l at 250 C [12]) seriously limits their application. To solve this
problem, the chemical functionalization of fullerene has been widely developed. Until now, a
large number of various fullerene derivatives have been synthesized, for example,
hydroxyfullerenes (fullerenols) with different numbers of hydroxyl groups [13–15], various
derivatives with carboxyl groups, some with fragments of crown ethers, and some with
amphiphilic polymer chains, hydrophilic porphyrins, calixarenes, and oligopeptides [12,16–19].

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Fullerenols С60(ОН)n are probably the most important among the various fullerene

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derivatives that are soluble in water. These substances have relatively simple molecular
structures and can contain up to forty hydroxyl groups. Their solubility depends on n and is 58.9
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g/l at pH 7 and n = 40 but drops when n decreases [13]. A complex analysis of the structure of
C60(OH)n fullerenol in aqueous solutions was performed recently using X-ray data, neutron
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scattering methods, and computer modelling [20]. These systems were characterized by
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supramolecular ordering when molecules were collected in primary chain-like aggregates of

several nanometres in length including 10-20 units. The combination of a hydrophobic carbon
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skeleton with a large number of hydrophilic hydroxyl groups should thus result in a noticeable
adsorption of fullerenols at the water surface when molecules contact each other via their
hydrophobic fragments, while their hydrophilic fragments predominantly interact with water.
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Currently, information on the surface properties of fullerenol solutions is scarce, likely

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due to a slight decrease in the surface tension of water even at relatively high concentrations
close to 1 g/l [15,21]. The formation of the adsorption layer of fullerenols with a small number of
hydroxyl groups (n = 12) has been confirmed via surface tensiometry, neutron reflectivity,
Brewster angle microscopy (BAM) and atomic force microscopy (AFM) [15]. It has been shown
that fullerenol adsorption leads to the formation of a monolayer with low surface pressures, but
the surface pressure increases significantly due to compression. After compression, relatively
fast relaxation can be observed at the initial surface pressure. No data on the adsorption layer
structure has been reported [15]. Only a slight decrease in the surface tension has been observed
for solutions of fullerenols with a relatively large number of hydroxyl groups (n = 30  2) in a
broad concentration range [21]. At the same time, the dilational dynamic surface elasticity of the
adsorption layer proved to be rather high, up to 170 mN/m, as a result of the aggregation in the
surface layer and the formation of multilayers at the interface.
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Results to date have shown that fullerenols with a large number of hydroxyl groups form
spontaneously rigid layers at the water interface and thereby can be used for the formation of
Langmuir – Blodgett films for technological applications. On the other hand, the surface activity
of fullerenols can strongly affect their interactions with biomembranes and must be considered in
medical applications. The information obtained until now relates only to two extreme cases of
highly hydrophobic and highly hydrophilic fullerenols, and the dependence of surface properties
on n remains unclear. This study investigates the properties of the adsorption layers of
fullerenols with an intermediate number of hydroxyl groups (n = 20), aiming to elucidate how
changes in this number influence the layer structure and properties.

Experimental

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Preparation of fullerenol C60(OH)20
Fullerene C60 (≥ 99.5 %) was obtained at the NRC Kurchatov Institute by a method
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described elsewhere [22]. The subsequent chromatographic purification required elimination of
fullerene oxide by activated carbon [23]. O-xylene, isopropanol and heptane (Lenreactiv, Russia)
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were distilled before use. Ammonium hydroxide, tetrabutylammonium hydrochloride, and
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hydrogen peroxide (Lenreactiv, Russia) were used as received.

The synthesis of fullerenol C60(OH)20 was carried out according to a scheme similar to
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that for the synthesis of a more hydrophilic C60(OH)30 and consisted of two main steps [24].
First, fullerene C60 was dissolved in o-xylene and mixed with a concentrated solution of
ammonium hydroxide in the presence of tetrabutylammonium hydrochloride as a catalyst. The
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mixture was stirred for 24 hours under slight heating without contact with air until complete
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discoloration of the organic phase occurred and a black suspension of low hydroxylated fullerene
(2  n  12) appeared. This fullerenol was separated from the solution, washed with o-xylene and
dried under a vacuum. The number of hydroxyl groups per molecule in the solid fraction was
confirmed by IR spectroscopy. Second, fullerenol with a low number of hydroxyl groups was
dissolved in water and subjected to further hydroxylation via the addition of hydrogen peroxide
in an anaerobic atmosphere at a temperature of 65-70 C for several hours. The product was
precipitated using a mixture of isopropanol/heptane at a ratio of 7/3, separated by centrifugation
and washed with a mixture of isopropanol/heptane to remove hydrogen peroxide. The thermal
analysis (Laboratory tube furnace SNOL 0.2/1250 with programmable thermostat, SNOL Term,
Russia) showed that fullerenol molecules contained 201 hydroxyl groups.
All aqueous solutions of fullerenol C60(OH)20 were prepared using triply distilled water.
In the second and third steps of distillation, an apparatus made of glass was used.
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The pH values of the solutions under investigation were acidic and slightly decreased
with increasing concentration from the values typical for water in dilute solutions up to 3.5 for
the highest concentration under investigation (0.5 g/l). The zeta-potential of colloidal species in
the entire concentration range was -40  2 mV.

Methods
The surface properties of the aqueous C60(OH)20 solutions were investigated via surface
tensiometry, surface dilational rheology, AFM, ellipsometry and BAM. The surface tension was
measured by the Wilhelmi plate method using polished glass, platinum and paper plates, and all
data with different plates coincided with an accuracy ± 0.2 mN/m. The following procedure was
used to estimate the changes of the properties of the plate in the course of measurements. The

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plate was removed from the balance in seven hours after the start of measurements, cleaned,

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placed back and brought into contact with the liquid surface. This procedure did not lead to
noticeable changes of the surface properties of the system under investigation.
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The dilational dynamic surface elasticity was measured via the oscillating barrier method
[25]. The fullerenol solution was poured into a rectangular polytetrafluoroethylene (PTFE)
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Langmuir trough with dimensions of 126×110×5 mm. The harmonic area oscillations of the
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liquid surface in the trough were created by a movable PTFE barrier with amplitudes of 2.5, 5,
and 7.5 % and at a fixed frequency of 0.1 Hz. If the adsorption layer was formed on the solution
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surface, the surface tension also varied according to the harmonic law. The ratio of the
amplitudes of the induced surface tension oscillations and of the surface area oscillations allowed
estimation of the dynamic surface elasticity modulus :
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⁄ ,
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where  is the surface tension, and S is the surface area.

The phase shift between the oscillations of the surface area and surface tension was near
zero in the error limits for all fullerenol solutions, and the adsorption layer was purely elastic.
The surface elasticity was determined every fifteen minutes, and five cycles of surface
compression-expansion were used for this purpose. The main results were obtained using the
lowest possible amplitude of the barrier oscillations (2.5 %). In this case, the system response to
surface area oscillations was almost linear and one can neglect the contribution of higher
harmonics to surface tension oscillations. Some examples of the surface tension oscillations at
different steps of the adsorption layer formation are presented in Fig. 2S of Supporting
Information.
The measurements of surface properties of C60(OH)20 solutions were repeated a few times
for all the concentrations. The accuracy of the surface tension was about 1 %, and that of the
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dynamic surface elasticity was about 5 % near equilibrium. The repeatability of the kinetic
dependencies was a little worse presumably due to the influence of uncontrolled convection in
the bulk phase on fullerenol diffusion to the interface.
The micromorphology of the adsorption layer was determined by atomic force
microscopy using an NTEGRA Prima instrument (NT-MDT, Russia). The adsorption layer of
fullerenol was transferred onto the surface of a freshly cleft mica plate by using the Langmuir-
Schaeffer and Langmuir-Blodgett methods. In the former case the mica plate was approached in
parallel the liquid surface and touched it. The excess of solution on the plate was removed
carefully by touching the edge of the plate by a piece of filter paper. After that, the mica plate
was dried for several days in a desiccator. The application of the Langmuir-Blodgett method to
adsorption films is described in detail in Ref. 26. The both methods resulted in similar AFM

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images of the films on the mica surface. Any possible slight differences can be connected with

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the peculiarities of the adsorption films but not of the transfer method. The AFM studies were
carried out in a semi-contact regime. The curvature radius of the cantilever was approximately
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10 nm.
A null ellipsometer (Optrel-GBR, Germany) with a wavelength of 623.8 nm was used to
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estimate the changes in the fullerenol surface concentration during adsorption. The
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measurements were carried out at angles of incidence near 50 (i.e., near the Brewster angle).
The difference between the ellipsometric angle Δ for the surface of pure water and for the
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surface of the one-component solution under investigation is approximately proportional to the

surface concentration [26].
The macroscopic morphology of the fullerenol adsorption layers on the solution surface
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was determined in situ by BAM using a BAM-1 instrument (NFT, Germany) equipped with a 10
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mV He-Ne laser. The solution was placed in a PTFE trough, and images of the solution surface
were taken at different adsorption steps.
The measurements of zeta-potential were carried out by using dynamic light scattering
with a Malvern Zetasizer device (Malvern Instruments, United Kingdom). Zeta-potential was
calculated according to the Smoluchovski equation:

where is the electrophoretic mobility; is the relative permittivity (dielectric constant); the
permittivity of vacuum and the viscosity. The relative uncertainty of the zeta-potential
determination was ± 5 %.
All the measurements were carried out at a constant temperature of 20  0.5 С.

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Results and discussion
The range of fullerenol concentration and the protocol of measurements in this study
were similar to those used in preceding work [21], where solutions of fullerenol with n = 30 were
investigated. Fig. 1 shows the kinetic dependencies of the surface tension and the dynamic
surface elasticity of С60(ОН)20 solutions at a concentration of 0.5 g/l, an oscillation frequency of
0.1 Hz and an oscillation amplitude of 2.5 %. The concentration dependence of surface tension
of solutions under investigation in 24 hours after surface formation is given in Supporting
Information (Fig. 1S).
The surface tension changed slowly and reached approximately 70 mN/m 6 hours after
surface formation. Similarly slow changes in surface tension have been observed for solutions of
fullerenols with few and many hydroxyl groups [15,21] and for solutions of fullerene derivatives

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with amino acids [27]. The induction period at the beginning of adsorption can indicate the

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heterogeneity of the adsorption layer [21,28]. In this case, the adsorbed molecules clump
together to form small non-interacting islands at the interface and do not affect the surface
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tension. When the number and size of the islands increase, they start to interact, and the surface
pressure and dynamic surface elasticity increase [21]. In С60(ОН)20 solutions at a concentration
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of 0.5 g/l, surface elasticity was near zero only during the first few minutes after the surface
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formation, unlike solutions of more hydrophilic С60(ОН)30. Surface elasticity then started to
increase and reached approximately 180 mN/m in an hour and approximately 300 mN/m in 22
hours (Fig. 1). These values were much higher than the dynamic surface elasticity of С60(ОН)30
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solutions due to the higher hydrophobicity of С60(ОН)20 fullerenol.

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continuous oscillations
400
70
periodic oscillations

, mN/m
65 300
, mN/m

60
200
compression
55

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100
50 expansion

45
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0 50 100 150 200 250 300 1400 1600 1800

t, min
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Fig. 1. Kinetic dependencies of the surface tension (red circles) and dynamic surface elasticity (black squares) of
С60(ОН)20 solutions with a concentration of 0.5 g/l, an oscillation frequency of 0.1 Hz and an oscillation amplitude
of 2.5 %. Thin arrows indicate the beginning of periodic oscillations in the surface area, the continuous oscillations
of the surface area, and the abrupt compression and expansion of the surface correspondingly.
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Six hours after surface formation, when the surface elasticity reached approximately 220
mN/m, the adsorption layer of С60(ОН)20 was transferred from the solution surface onto the
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surface of mica by using the Langmuir – Shaeffer method and was then investigated by AFM
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(Fig. 2a).
Fig. 2a shows that the fullerenol film consisted of more than one molecular layer. Each
layer was formed by closed packed molecules and separate disc-like aggregates with a diameter
in the range from a few nanometres up to about fifty nanometres. The thickness of the layers was
between 0.5 and 1 nm and was thus close to the size of fullerenol molecules. The thickness of the
surface aggregates could reach 3 nm. The obtained high dynamic surface elasticity is typical for
surface films of closed packed solid nanoparticles on aqueous subphases and probably occurred
due to the formation of rigid multilayers [29,30].

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а) b)

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c) d)
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Fig. 2. AFM images of С60(ОН)20 layers transferred onto the surface of mica: a) 6 hours after the surface formation;
b) an hour after the beginning of continuous oscillations; c) an hour after surface compression; and d) an hour after
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surface expansion up tо the initial surface.

When the measurements were stopped, surface elasticity continued to increase during the
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subsequent sixteen hours without external mechanical perturbations (Fig. 1). Large changes in
surface elasticity during the twenty two hours of measurements were accompanied by only a
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slight decrease of approximately 3 mN/m in surface tension. Then, the adsorption layer was
transferred onto the mica surface before further measurements were performed. In this case,
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AFM images of the layer were similar to those shown in Fig. 2a and indicated only a slight
decrease in aggregate concentration. The subsequent beginning of periodic oscillations of the
surface area (five periods of oscillations for every 15 minutes) did not result in noticeable
changes in surface elasticity. Then, the continuous oscillations of the surface area began, and the
dynamic surface elasticity began to decrease to approximately 220 mN/m. The continuous
oscillations of the surface area also caused an increase of approximately 1 mN/m in surface
tension. Such a response of the adsorption layer to oscillations of the surface area have not been
observed earlier in solutions of conventional surfactants, amphiphilic polymers or aqueous
dispersions of soft nanoparticles [25,31–33] but is characteristic of aqueous dispersions of solid
nanoparticles [29,30]. This feature can be connected with partial destruction of a fragile
fullerenol layer via mechanical perturbations of the liquid surface. Similar behaviour has been

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observed before in С60(ОН)30 solutions [21] but not in solutions of fullerene derivatives with
arginine and lysine [27], indicating the high sensitivity of the hydroxyfullerene layers to surface
oscillations. The AFM data confirm this conclusion. The AFM image of the layer transferred
onto the surface of mica after switching off continuous oscillations showed a large number of
separate aggregates and empty places between them, which were presumably formed under the
action of these oscillations (Fig. 2b). The surface layer became looser, and the dynamic surface
elasticity decreased by approximately 25 % compared with the values before the beginning of
continuous oscillations.
The compression of the surface of fullerenol solution by 50 % resulted in an abrupt drop
of the surface tension to 47 mN/m and the dynamic surface elasticity to 175 mN/m (Fig. 1). The
subsequent relaxation for one hour led to only a slight increase in the surface elasticity to 183

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mN/m but to a more significant increase in the surface tension up to 60 mN/m. This behaviour

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differed from the corresponding results for С60(ОН)30 solutions, where surface compression
resulted in an increase in the dynamic surface elasticity [21]. This effect for С60(ОН)30 solutions
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was connected with some structural rearrangements, leading to more compact packing in the
surface layer. In the case of the С60(ОН)20 adsorption layer, the AFM images indicate the
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formation of elongated aggregates after compression (Fig. 2c). Their characteristic length was
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approximately 100 nm, and their thickness exceeded 10 nm. These dimensions are about one
order of magnitude higher than those of the surface aggregates before compression. The
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simultaneous formation of some regions of low density between the elongated aggregates can
explain the decrease in the dynamic surface elasticity after compression despite the increase in
the total surface concentration. The observed aggregates may be formed in the course of a local
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collapse of the adsorption layer upon compression, which can result in the formation of some
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patches of multilayers. Similar morphology of the adsorption layer has been observed in mixed
solutions of sodium polystyrenesulfonate and dodecyltrimethylammonium bromide after an
increase in the surfactant concentration above a certain critical value [34].
The subsequent expansion of the surface in the Langmuir trough to the initial area
resulted in an abrupt increase in surface tension up to the value for pure water; the dynamic
surface elasticity also dropped simultaneously almost to zero (Fig. 1). Then, the surface elasticity
returned to the values before expansion for less than an hour, and the surface tension approached
the value for an unperturbed surface. Presumably, the adsorption layer after expansion breaks
down into separate islands (surface aggregates) that do not interact and thereby do not affect the
surface properties. Gradually, these large aggregates spread along the surface, which can be
accompanied by further fullerene adsorption and lead to a decrease in surface tension and an
increase in dynamic surface elasticity. AFM allows us to observe many aggregates in the surface
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layer in an hour after surface expansion (Fig. 2d), and they resemble the surface aggregates in
Fig. 2b.
The decrease in fullerene concentration resulted in a strong deceleration of the changes in
surface properties. The surface tension decreased by not more than 1 mN/m 30 hours after
surface formation at С60(ОН)20 concentrations less than 0.3 g/l. Fig. 3 shows the corresponding
kinetic dependencies of the dynamic surface elasticity at concentrations of 0.5, 0.1 and 0.03 g/l.

300 periodic oscillations

expansion

of
250
, mN/m

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200

continuous oscillations
150
-p
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100 compression
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50
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0
0 100 200 300 1400 1600 1800

t, min
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Fig. 3. Kinetic dependencies of the dynamic surface elasticity of С60(ОН)20 solutions at a frequency of 0.1 Hz, an
oscillation amplitude of 2.5 % and concentrations of 0.5 (black squares), 0.1 (red circles), and 0.03 g/l (green
triangles). Thin arrows indicate the beginning of periodic oscillations of the surface area, continuous oscillations of
the surface area, and the abrupt compression and expansion of the surface correspondingly.

The dynamic surface elasticity of the solution with a concentration of 0.03 g/l was zero
within error limits. There was a long induction period at a concentration of 0.1 g/l (Fig. 3). The
dynamic surface elasticity was near zero for two hours and then increased slowly, reaching
approximately 75 mN/m after 7 hours and 200 mN/m after 17 hours without surface oscillations.
The beginning of the oscillations resulted in a slight decrease (approximately 10 mN/m) for less
than one hour. The application of continuous oscillations led to a decrease of 20 %, as in the case
of subsequent surface compression. At a concentration of 0.5 g/l, the kinetic dependence of the
dynamic surface elasticity and the response to external mechanical perturbations were

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qualitatively the same, but the surface elasticity changed faster and approached 305 mN/m for 22
hours after surface formation.
The dynamic surface elasticity of the investigated С60(ОН)20 solutions reached steady-
state values approximately 24 hours after the surface formation, unlike in the case of С60(ОН)30
when the surface properties changed for a few days after surface formation [21]. The surface
properties of С60(ОН)20 solutions changed after more than 24 hours only due to external
mechanical perturbations in the adsorption layer.

250

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200

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periodic oscillations
|  |, mN/m

150
-p
re
100
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50 continuous oscillations
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0
0 100 200 300 1400 1600
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t, min
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Fig. 4. Kinetic dependencies of the dynamic surface elasticity for С60(ОН)20 solutions at a concentration of 0.1 g/l, a
frequency of 0.1 Hz and relative amplitudes of the surface area oscillations of 2.5 % (red circles), 5 % (black
squares) and 7.5 % (green triangles). Thin arrows indicate the beginning of periodic and continuous oscillations of
the surface area.

The induction period decreased, and the dynamic surface elasticity changed faster when
oscillation amplitude increases from 2.5 to 7.5 % (Fig. 4). The observed distinctions were likely
caused by the enhanced convection in the solution due to surface oscillations with higher
amplitudes. The beginning of the oscillations after a quiet period resulted in a faster and stronger
drop in the surface elasticity at higher oscillation amplitudes due to faster degradation of the
fragile adsorption layer.
The ellipsometric angle Δ, which is approximately proportional to the surface
concentration, approached steady-state values faster than the surface tension and dynamic
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surface elasticity for both С60(ОН)20 and С60(ОН)30 solutions (Fig. 5) [21]. The main changes in
the ellipsometric angle occurred for approximately 1 hour after surface formation, and all
changes after that were near the error limits at a concentration of 0.5 g/l. The equilibration time
increased when the concentration decreased.

of
3
, grad

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2 -p
1
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0
0 200 400 600 800 1000 1200
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t, min
Fig. 5. Kinetic dependencies of ellipsometric angle Δ at С60(ОН)20 concentrations: 0.5 (red circles), 0.1 (black
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squares) and 0.03 g/l (green triangles).

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The observed distinctions between the rates of relative changes in the ellipsometric angle
and the dynamic surface elasticity mean that slight changes in the surface concentration at the
approach to equilibrium can result in significant structural changes in the adsorption layer and
thereby in noticeable changes in the surface rheological properties. Note that Δ values in Fig. 5
are higher than the corresponding results for С60(ОН)30 solutions [21], which is indicative of the
higher surface concentration of a more hydrophobic fullerenol. At a concentration of 0.03 g/l, Δ
was near zero, and one can observe only a few fluctuations in the angle. However, average
results in non-zero values indicate adsorption layer formation. The observed fluctuations can be
connected with the macroscopic heterogeneity of the adsorption layer and its mobility in the case
of low surface concentration.
The heterogeneity of the adsorption layer of С60(ОН)20 at a concentration of 0.03 g/l is
shown using BAM, while the macroscopically homogeneous adsorption layer was formed a few
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minutes after surface formation at higher concentrations; layer morphology did not change after
that (Fig. 6).

а) b)

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c) d)
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e) f)
Fig. 6. BAM images of the С60(ОН)20 layer а) 0.02; b) 0.25; c) 2.5; d) 10 hours after surface formation; e) at a
surface compression of 50 %; and f) at subsequent surface expansion to the initial area.

Surface aggregates were formed 1 minute after surface formation (right hand corner of
the image in Fig. 6а). After 15 minutes, almost the whole field was covered by aggregates, which
were in permanent motion (Fig. 6b). The surface pressure and elasticity were near zero (Fig. 3),
but the ellipsometric angle Δ differed from that of water (Fig. 5). The areas free from surface
aggregates decreased gradually and almost disappeared 2.5 hours after surface formation (Fig.
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6c), but the adsorption layer preserved its mobility. The surface appeared to be macroscopically
homogeneous after ten hours (Fig. 6d). This adsorption step corresponded to a constant surface
elasticity and slight changes in the ellipsometric angle (Fig. 5). Layer morphology remained
relatively consistent after a surface compression of 50 % (Fig. 6e). At the same time, surface
mobility decreased, but surface rheological properties did not change. Immediately after surface
expansion to the initial surface area, both areas were covered by the fullerenol layer (the lower
right hand corner of Fig. 6f) and the areas free from the adsorption layer (the upper left hand
corner of Fig. 6f); however, the layer became more homogeneous after 10 to 15 minutes.

Conclusions
Fullerenol C60(OH)20 forms a macroscopically homogeneous layer at the solution-air

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interface, similar to the more hydrophilic fullerenol C60(OH)30. In both cases, slight changes in

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surface tension (approximately 5 mN/m) are accompanied by a strong increase in the dynamic
surface elasticity. At the same time, surface elasticity is much higher for C60(OH)20 solutions and
-p
is approximately 300 mN/m compared to 135 mN/m for C60(OH)30 solutions at a concentration
of 0.5 g/l. The rigid adsorption layer can be easily transferred onto a solid surface by using the
re
Langmuir-Blodgett and Langmuit-Schaeffer methods. Adsorption kinetics are faster for
lP

C60(OH)20 solutions presumably due to a lower charge of molecules and thus a lower adsorption
barrier. The surface properties of fullerenol solutions are sensitive to small mechanical
na

perturbations in the interface. The adsorption layer of C60(OH)20 is more fragile than that of
C60(OH)30, and surface compression results in a drop in the dynamic surface elasticity by
approximately 25 % in the former case, while in the latter case, the surface elasticity increases
ur

after compression. Continuous oscillations of the surface area also lead to a decrease in the
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surface elasticity due to the partial degradation of the adsorption layer. Atomic force microscopy
allows us to track adsorption layer degradation under mechanical perturbations and shows that
the layer is not a monolayer of fullerenol molecules. The layer is also not homogeneous at the
microscopic scale but contains small surface aggregates. Brewster angle microscopy shows that
the adsorption layer contains separate macroscopic surface aggregates at the beginning of
adsorption at low C60(OH)20 concentrations but becomes more homogeneous a few hours after
surface formation.

Acknowledgements

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This study was financially supported by RFBR, project nos. 18-29-19100. The authors are also
grateful to the Centre for Diagnostics of Functional Materials for Medicine, Pharmacology and
Nanoelectronics, and Chemical Analysis and Materials Research Centre of St. Petersburg State
University.

Appendix A. Supplementary data

Supplementary data to this article can be found online at:

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References
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Figure legends

Fig. 1. Kinetic dependencies of the surface tension (red circles) and dynamic surface elasticity
(black squares) of С60(ОН)20 solutions with a concentration of 0.5 g/l, an oscillation frequency of
0.1 Hz and an oscillation amplitude of 2.5 %. Thin arrows indicate the beginning of periodic
oscillations in the surface area, the continuous oscillations of the surface area, and the abrupt
compression and expansion of the surface correspondingly.

Fig. 2. AFM images in С60(ОН)20 layers transferred onto the surface of mica: a) 6 hours after the
surface formation; b) an hour after the beginning of continuous oscillations; c) an hour after
surface compression; and d) an hour after surface expansion up tо the initial surface.

Fig. 3. Kinetic dependencies of the dynamic surface elasticity of С60(ОН)20 solutions at a

frequency of 0.1 Hz, an oscillation amplitude of 2.5 % and concentrations of 0.5 (black squares),

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0.1 (red circles), and 0.03 g/l (green triangles). Thin arrows indicate the beginning of periodic
oscillations of the surface area, continuous oscillations of the surface area, and the abrupt
compression and expansion of the surface correspondingly.

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Fig. 4. Kinetic dependencies of the dynamic surface elasticity for С 60(ОН)20 solutions at a
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concentration of 0.1 g/l, a frequency of 0.1 Hz and relative amplitudes of the surface area
oscillations of 2.5 % (red circles), 5 % (black squares) and 7.5 % (green triangles). Thin arrows
indicate the beginning of periodic and continuous oscillations of the surface area.
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Fig. 5. Kinetic dependencies of ellipsometric angle Δ at С60(ОН)20 concentrations: 0.5 (red

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circles), 0.1 (black squares) and 0.03 g/l (green triangles).

Fig. 6. BAM images of the С60(ОН)20 layer а) 0.02; b) 0.25; c) 2.5; d) 10 hours after surface
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formation; e) at a surface compression of 50 %; and f) at subsequent surface expansion to the

initial area.
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Declaration of competing interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

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Authorship contribution statement

Alexander V. Akentiev: Analysis of AFM Images, Writing - review & editing. Sofiia B.
Gorniaia: Analysis of BAM images, Writing - review & editing. Nikolaj A. Isakov:
Methodology, Writing - review & editing. Vasylij T. Lebedev: Investigation, Methodology,
Writing - review & editing. Olga Yu. Milyaeva: Analysis of ellipsometric data and surface
rheological data. Victor P. Sedov: Fullerenol synthesis and analysis. Konstantin N. Semenov:
Fullerenol purification and analysis. Kirill A. Timoshen: Rheological measurements,
Investigation. Boris A. Noskov: Investigation, Writing – editing.

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Graphic abstract

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Highlights.

Fullerenols form macroscopically homogeneous layers at the solution-air interface.

The fullerenol adsorption layer can be easily transferred onto solid surface by the Langmuir-
Schaeffer method.
The surface properties of fullerenol solutions are very sensitive to small mechanical
perturbations.
The adsorption layer of C60(OH)20 is more fragile than that of C60(OH)30.

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