Materials Science and Engineering C 60 (2016) 184–194

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Materials Science and Engineering C

journal homepage: www.elsevier.com/locate/msec

Photocatalytic self-cleaning poly(L-lactide) materials based on a hybrid

between nanosized zinc oxide and expanded graphite or fullerene
Daniela Virovska a, Dilyana Paneva a,⁎, Nevena Manolova a, Iliya Rashkov a,⁎, Daniela Karashanova b
a
Laboratory of Bioactive Polymers, Institute of Polymers, Bulgarian Academy of Sciences, Acad. G. Bonchev St., bl. 103A, BG-1113 Sofia, Bulgaria
b
Institute of Optical Materials and Technologies, Bulgarian Academy of Sciences, Acad. G. Bonchev St., bl. 109, BG-1113 Sofia, Bulgaria

a r t i c l e i n f o a b s t r a c t

Article history: New self-cleaning materials of polymer fibers decorated with a hybrid between nanosized zinc oxide and ex-
Received 27 August 2015 panded graphite (EG) or fullerene (C60) were obtained. The new materials were prepared by applying
Received in revised form 9 October 2015 electrospinning in conjunction with electrospraying. Poly(L-lactide) (PLA) was selected as a biocompatible and
Accepted 11 November 2015
(bio)degradable polymer carrier. PLA solution was electrospun in combination with electrospraying of a suspen-
Available online 11 November 2015
sion that contained the ZnO/EG or ZnO/C60 hybrid. Mats with different content of EG or C60 were obtained. The
Keywords:
new materials were characterized by scanning and transmission electron microscopy (SEM and TEM), energy-
Electrospinning dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis
Electrospraying (TGA), differential scanning calorimetry (DSC) and X-ray diffraction analysis (XRD). The photocatalytic activity
Self-cleaning materials of the materials was evaluated by using model dyes. The formation of a hybrid between ZnO and EG led to en-
Poly(L-lactide) hancement of the photocatalytic activity of the mats at ZnO/EG weight ratios of 90/10 and 85/15. Increase in
ZnO the photocatalytic activity of the ZnO-containing mats was also achieved by the formation of a hybrid between
Expanded graphite ZnO and C60 at a fullerene content of 0.5 and 1.0 wt.% in respect to ZnO weight. The new materials exhibited an-
Fullerene
tibacterial activity as evidenced by the performed studies against Staphylococcus aureus.
Hybrid
© 2015 Elsevier B.V. All rights reserved.
Photocatalytic activity
Antibacterial activity

1. Introduction the photogenerated electron–hole pairs leading to a decrease of their

Recently the self-cleaning materials evoke significant interest due to
the increased demand for design of new generation hygienic, self-
disinfecting and contamination-free surfaces [1]. Special attention has
been paid to self-cleaning materials based on zinc oxide and titanium
dioxide [2]. This is attributed to the extremely useful ability of these
semiconductors under UV irradiation to degrade a great variety of or-
ganic substances, e.g. dyes that are waste products from the textile in-
dustry [3–5]. In addition, another valuable feature is the antibacterial
activity of these oxides.
It is known that the photocatalytic and antibacterial activity of zinc
oxide is due to the formation under UV irradiation of oxidized holes
and reduced electrons. The latter interact with the water molecules
and lead to the formation of hydroxyl radicals and other reactive oxygen
species that are responsible for causing degradation of organic sub-
stances and killing of pathogenic microorganisms. Thus, regarding
these activities of zinc oxide the efficiency of electron–hole pair forma-
tion is of essential importance. The main disadvantage of zinc oxide and
titanium dioxide is the occurrence of a rapid process of recombination of
⁎ Corresponding authors.
E-mail addresses: panevad@polymer.bas.bg (D. Paneva), rashkov@polymer.bas.bg
(I. Rashkov).
photocatalytic activity [6]. Thus, in recent years various approaches
have been developed in order to prevent this undesired recombination,
e.g. preparation of a hybrid between the semiconductor and a noble
metal (Au, Pt, Pd). Use of a noble metal is a costly solution. This necessi-
tates finding additives that would substitute for the noble metals. There
are reports on the use of the allotropic forms of carbon — graphite,
graphene and fullerene (C60), as an attractive alternative to the noble
metals in order to enhance the photocatalytic activity of the zinc oxide
[7–13]. The increase in the photocatalytic activity of the zinc oxide in
the presence of the aforementioned allotropic forms of carbon is attrib-
uted to a transfer of an electron from the zinc oxide to the graphite,
graphene or C60. The above cited reports are on evaluation of the prop-
erties of the hybrid zinc oxide/allotropic form of the carbon in the form
of a powder, film or suspension. These forms of application are difficult
to handle. This requires the development of new solutions for loading
this type of hybrids in a polymer carrier in order to facilitate the han-
dling of these materials for certain applications.
• The electrospinning has become an extremely promising method
for preparation of fibrous materials that can serve as carriers for di-
verse in nature metal nanoparticles (e.g., silver nanoparticles) and
nanosized metal oxides (like titanium dioxide and zinc oxide) [6,
14–19]. The combination of electrospinning and electrospraying

http://dx.doi.org/10.1016/j.msec.2015.11.029
0928-4931/© 2015 Elsevier B.V. All rights reserved.
 D. Virovska et al. / Materials Science and Engineering C 60 (2016) 184–194
techniques provides a main benefit in terms of the design of hybrid
material polymer/nanosized metal oxide, i.e. the oxide deposits
only on the fiber surface and is not located in the fiber bulk [20,21].
Recently, we have shown that the fibrous materials prepared by
electrospinning of a solution from poly(L-lactide) and electrospraying
of a suspension of nanosized zinc oxide have much better photocata-
lytic behavior as compared to fibrous materials prepared by
electrospinning of a PLA/ZnO suspension [22]. Thus, in the present
study the electrospinning/electrospraying technique was selected
for the design on the new self-cleaning PLA/ZnO/EG or PLA/ZnO/C60
materials.
To our knowledge, fibrous polymer materials decorated with zinc
oxide/graphene hybrid have not yet been reported. There are no data
on incorporation of ZnO/C60 hybrid in fibrous materials by
electrospinning or electrospinning/electrospraying. Nanofibers from
TiO2–ZnO–graphene and graphene-decorated ZnO nanofibers have
been prepared using electrospinning of blends with a polymer (polyvi-
nylpyrrolidone or polyacrylonitrile) [23,24]. In both studies the polymer
has been utilized as a sacrificial template, and the final inorganic fibers
have been obtained after calcination of the electrospun polymer materi-
al. The materials obtained after the calcination are not easy to handle.
The aim of the present study was to evaluate the possibility to apply
electrospinning in conjunction with electrospraying for preparation of
photocatalytic self-cleaning materials from poly(L-lactide) fibers deco-
rated with a hybrid between nanosized zinc oxide and EG or C60, looking
for improved photocatalytic activity as compared to mats from PLA/
nanosized zinc oxide. PLA was selected as a polymer partner because
of its biocompatibility and its susceptibility to hydrolytic and enzymatic
degradation [25]. The photocatalytic activity of the obtained fibrous ma-
terials was evaluated spectrophotometrically by using two model dyes.
The behavior of the new materials in contact with pathogenic microor-
ganisms was assessed against Staphylococcus aureus.
2. Experimental
2.1. Materials
Poly(L-lactide) (PLA) was a commercial product (INGEO™ Bio-
polymer 4032D, NatureWorks LLC — USA) having MW = 259,000 g/
mol and Đ = 1.94 as determined by size-exclusion chromatography
using polystyrene standards. The used nanosized zinc oxide and zinc
oxide with silanized surface are commercial products available
under the trade mark Zano®20 and Zano®20 Plus, respectively. The ex-
panded graphite (EG) available under the trade mark TIMREX BNB 90
was supplied by Timcal Belgium S.A. Fullerene (C60, 98%) was pur-
chased from Sigma-Aldrich and used as received. Chloroform, N,N-
dimethylformamide (DMF) and toluene were of analytical grade, and
were purchased from Merck. Methylene Blue (MB) dye was purchased
from Merck, and Reactive Red (CI Reactive Red 1, RR) was kindly sup-
plied by Prof. T. Konstantinova, UCTM-Sofia. Staphylococcus aureus 749
(S. aureus) was purchased from the National Bank for Industrial Micro-
organisms and Cell Cultures, Sofia, Bulgaria.
2.2. Preparation of PLA/ZnO/EG materials by electrospinning/
electrospraying
Zano®20 nanosized zinc oxide was used for the preparation of the
PLA/ZnO/EG materials. The mats were prepared by combined utilization
of electrospinning and electrospraying using the following equipment:
two pumps [NE-300 Just Infusion™ Syringe Pump (New Era Pump Sys-
tems Inc., USA); for delivering the PLA spinning solution and the
suspension from EG/PLA, ZnO/PLA or ZnO/EG/PLA, respectively; the
pumps were arranged at an angle of 180° in respect to the collector], a
rotating aluminum collector for deposition of PLA fibers and of EG,
185
ZnO or EG/ZnO and a high-voltage power supply (up to 30 kV). For
the electrospinning, a PLA solution of 10 wt.% in a mixed solvent chloro-
form/DMF = 3.7/1 (v/v) was used. For the electrospraying, the ZnO con-
tent of 20% (w/v), as well as the PLA additive content of 0.05% (w/v),
were kept constant. The PLA additive served as a sticking agent for
ZnO, EG or ZnO/EG on the fiber surface. EG content in the suspension
was varied, and ZnO/EG ratio was 95/5, 90/10 or 85/15 (w/w), respec-
tively. For preparation of the suspension for electrospraying, EG
(0.063, 0.13 or 0.21 g) was dispersed in 3 ml DMF for 15 min using an
electromagnetic stirrer, then ZnO (1.2 g) was added. The obtained sus-
pension was agitated for 2 h using an electromagnetic stirrer and soni-
cated for 15 min in an ultrasonic bath Bandelin Sonorex, 160/640 W,
35 kHz. After that PLA solution in chloroform (0.003 g in 3 ml) was
added into ZnO/EG suspension and the as-prepared suspension was
sonicated for 30 min. The mats that contain the ZnO/EG hybrid at a
weight ratio of 95/5, 90/10 or 95/15 are further designated as [ZnO/
EG5]-on-PLA, [ZnO/EG10]-on-PLA and [ZnO/EG15]-on-PLA, respective-
ly. Mats, containing ZnO or EG alone, were prepared as controls and
were designated as ZnO-on-PLA and EG-on-PLA, respectively.
The preparation of the materials by electrospinning/electrospraying
was performed under the following conditions: applied voltage of
25 kV; needle tip-to-collector distance of 17 cm and 13 cm for the
electrospinning and electrospraying, respectively; the delivery rate of
PLA spinning solution was 2 ml h− 1, and of the suspension —
3 ml h−1; rotating rate of the collector 1900 rpm; temperature 25 °C.
2.3. Preparation of PLA/ZnO/C60 materials by electrospinning/
electrospraying
Zano®20 Plus nanosized zinc oxide was used for the preparation of
PLA/ZnO/C60 materials. The mats were prepared by combining
electrospinning and electrospraying techniques, using the same equip-
ment as in the case of PLA/ZnO/EG mats. For the electrospinning
10 wt.% solution of PLA in chloroform/DMF = 3.7/1 (v/v) mixed solvent
was used. The ZnO content of 10% (w/v), and the sticking agent (PLA)
content of 0.05% (w/v) were kept constant in the suspension for the
electrospraying. The C60 content was varied: 0.25, 0.5, 1.0, 1.4, 2.0 and
2.5 wt.% in respect to ZnO weight. Further, the PLA/ZnO/C60 samples
are designated as follows: [ZnO/C600.25]-on-PLA, [ZnO/C600.5]-on-PLA,
[ZnO/C601.0]-on-PLA, [ZnO/C601.4]-on-PLA, [ZnO/C602.0]-on-PLA and
[ZnO/C602.5]-on-PLA. The suspension for electrospraying was prepared
by dissolving the necessary amount of C60 in 3 ml toluene and sonica-
tion for 30 min using ultrasonic bath Bandelin Sonorex, 160/640 W,
35 kHz. ZnO (0.6 g) was added to the as-prepared solution under con-
tinuous stirring with magnetic stirrer and the suspension was sonicated
for 15 min. Then 0.05% (w/v) PLA solution in chloroform (3 ml) was
added and the suspension was additionally sonicated for 15 min.
The preparation of the materials by electrospinning/electrospraying
was performed under the following conditions: applied voltage
of 25 kV; tip-to-collector distance of 17 cm and 15 cm for the
electrospinning and electrospraying, respectively; delivery rate of
3 ml h−1 for PLA solution and for the suspension; rotating rate of the
collector 1900 rpm; temperature 25 °C.
2.4. Material characterization
The morphology of the materials was evaluated by scanning electron
microscopy (SEM). The samples were vacuum-coated with gold prior to
observation by SEM (Jeol JSM-5510 or Philips SEM 515). The mean fiber
diameter was estimated by ImageJ software, and their morphology was
assessed applying the criteria for evaluation of electrospun materials as
described in detail in [26]. TEM observations were carried out by JEM
2100 (JEOL Co. Ltd.) operating at a voltage of 200 kV. The samples
were prepared by depositing on a copper grid. The elemental analyses
of the materials were performed using JEM 2100LaB6 (JEOL Co. Ltd.)
equipped with energy-dispersive X-ray spectrometer (EDX). The
186 D. Virovska et al. / Materials Science and Engineering C 60 (2016) 184–194
surface chemical composition of the materials was determined by X-ray
photoelectron spectroscopy (XPS). The XPS measurements were carried
out in the UHV chamber of an ESCALAB-MkII (VG Scientific) spectrom-
eter using Mg Kα excitation with a total resolution of ca. 1 eV. Energy
calibration was performed taking the C 1s line at 285 eV as a reference.
The thermal stability of the fibrous materials and ZnO content were
determined by thermogravimetry using TA Instrument TGA Q5000 in
nitrogen. The heating was from r.t. to 1000 °C at a heating rate of 10
°C min−1. Differential scanning calorimetry (DSC) analyses were per-
formed using a Perkin Elmer DSC 8500 apparatus in nitrogen
atmosphere at a heating rate of 10 °С min−1. PLA crystallinity degree
(χPLA
c , %) was calculated using the equation:
h

i
χ c PLA ; % ¼ ΔH m PLA −ΔHcc PLA = ΔHm PLA;0  W PLA  100
where WPLA is PLA weight fraction in the fibrous material; ΔH0m is the
heat of fusion of 100% polymer crystal: ΔHPLA,0
m = 93.0 J g−1 [27].
X-ray diffraction (XRD) analyses were performed at r.t. using a
computer-controlled D8 Bruker Advance ECO powder diffractometer
with filtered Cu Kα radiation. Data were collected in the 2θ range
from 5° to 80° with a step of 0.02° and counting time of 1 s step−1.
2.5. Assessment of the photocatalytic activity of the new materials in respect
to Methylene Blue and Reactive Red dyes
For assessment of the photocatalytic activity of the prepared new
materials Methylene Blue (MB) and Reactive Red (RR) were used as
model dyes. The samples' weight was selected in such a manner so
that ZnO content would be 0.8 mg. The samples were immersed in
7 ml aq. solution of MB (2 × 10− 5 mol l− 1) or RR
(6.3 × 10−5 mol l−1) and kept for 30 min in the dark. After that they
were irradiated with UV–visible light (UVASPOT 400/T, Dr. Honle AG;
UV lamp UV 400 F/2; 400 W; wavelength range: from 260 to 600 nm;
Fig. 1. SEM micrographs of PLA fibers and ZnO/EG particles on their surface observed in the case of [ZnO/EG10]-on-PLA mat prepared by combined electrospinning/electrospraying (A, B).
SEM micrograph of spherical ZnO aggregates on the surface of EG flake (C).
λmax = 385 nm) for 5 h. During the experiments the temperature of
the solutions was kept at 20 °С using a LAUDA PE 104 thermostat. The
photocatalytic decomposition of MB and RR was followed using
DU800 spectrophotometer (Beckman Coulter, Inc.) at 660 nm and
532 nm, respectively, by recording the decrease in the absorbance of
MB or RR in the presence of the new materials as a function of the irra-
diation time. The presented data are average values from 3 measure-
ments. The apparent rate constant (Kapp) was calculated from the
kinetic curves of the dye degradation: ln(CMB o
or RR
/ CMB or RR) = f(t),
MB or RR
where Co was the initial concentration of MB or RR, CMB or RR —
the concentration of MB or RR at the moment t, and t was the irradiation
time. Kapp was calculated from the dependence ln(CMB o
or RR
/ CMB or
RR
) = Kapp × t [22,28]. The reusability of the materials was tested by im-
mersing them into a fresh MB or RR solution after a catalysis run; before
ð1Þ
each replacement of the dye solution the mats were washed three times
with distilled water. This procedure was repeated three times for each
sample.
2.6. Microbiological assessment of the antibacterial activity of [ZnO/EG]-on-
PLA and [ZnO/C60]-on-PLA mats against S. aureus
The antibacterial activity of ZnO-on-PLA, [ZnO/EG10]-on-PLA, [ZnO/
EG15]-on-PLA, [ZnO/C600.5]-on-PLA and [ZnO/C601.0]-on-PLA mats
was assessed against the Gram-positive microorganism S. aureus by
counting the number of surviving cells. Bacterial suspension of 10-
5
cells ml−1 was used. The samples' weight was selected in such a man-
ner so that the zinc oxide concentration in the bacterial suspension
(2 ml) would be above the minimum inhibitory concentration (MIC)
of zinc oxide against S. aureus. The MIC of zinc oxide against this micro-
organism is 0.5 mg ml− 1 [29]. The samples were placed in six-well
plates, and the bacterial suspension was added to each well.
The pathogenic microorganisms' growth was evaluated under con-
tinuous irradiation by a 10 W lamp at a wavelength λ = 420 nm. The
distance between the lamp and the six-well plate was 10 cm. At
 D. Virovska et al. / Materials Science and Engineering C 60 (2016) 184–194
predetermined time intervals (2, 4 and 24 h) aliquots were taken from
the bacterial suspension and several decimal dilutions were made. The
surviving microorganisms were counted by the spread-plate method
in triplicate for each experiment. The number of the surviving cells
was determined as colony forming units (CFU). The presence of adhered
S. aureus cells after their 24-h contact with the mats was evaluated by
SEM. For that purpose after the 24-h contact the mats were washed
twice with phosphate buffered saline (PBS, pH 7.4) for removal of
non-adhered bacteria. The adhered bacteria on the surface of the mats
were fixed by immersion of the mats in 2.5 wt.% glutaraldehyde solution
in PBS at 4 °C for 5 h. Then the samples were washed again carefully
with PBS and freeze-dried. Prior to the SEM observation the mats
were coated with carbon and gold.
3. Results and discussion
3.1. PLA/ZnO/EG materials prepared by conjunction of electrospinning and
electrospraying
Conditions for preparation of [ZnO/EG]-on-PLA materials at a ZnO/
EG ratio of 95/5, 90/10 or 85/15 (w/w) by electrospinning/
electrospraying were found. SEM micrographs of [ZnO/EG10]-on-PLA
prepared by simultaneous electrospinning of a PLA solution and
electrospraying of a ZnO/EG suspension that contains 0.05% (w/v) of
PLA are presented in Fig. 1. The latter served as a sticking agent for
ZnO and EG on the fiber surface to prevent their loss during the handling
Fig 2. A SEM micrograph and EDX mapping images of C, O and Zn of a single [ZnO/EG10]-on-PLA fiber (A) and detailed C 1s (B), O 1s (C) and Zn 2p3/2 (D) spectra registered by XPS for [ZnO/
EG10]-on-PLA mat.
187
of the produced materials. It was found that [ZnO/EG]-on-PLA mats
were composed of PLA fibers with a mean diameter of 1.70 ±
0.26 μm, EG flakes and spherical ZnO aggregates. As seen from Fig. 1B
and C, ZnO was deposited on the fibers as well as on the EG flake surface.
The analyses of the spherical ZnO aggregate morphology showed that
the incorporation of EG in the suspension did not alter their mean diam-
eter values (ca. 1 μm). As expected, the EDX analyses revealed that the
new materials were composed of C, O and Zn (Fig. 2A).
The surface composition of ZnO-on-PLA, EG-on-PLA and [ZnO/EG]-
on-PLA mats was studied by XPS. Carbon and oxygen at 285 eV and
530 eV were detected in the XPS survey spectra of PLA and EG-on-PLA
mats. For ZnO-on-PLA and [ZnO/EG]-on-PLA mats the presence of zinc
at 1023 eV was detected as well and its content in ZnO-on-PLA, [ZnO/
EG5]-on-PLA, [ZnO/EG10]-on-PLA and [ZnO/EG15]-on-PLA mats was
10%. The detailed spectra of C 1 s, O 1 s and Zn 2p3/2 registered for
[ZnO/EG10-on-PLA] material by XPS are presented in Fig. 2B–D. Peaks
at 289 eV, 287 eV and 285 eV were detected in the C 1s spectrum and
were attributed to carbon atoms engaged in O–C_O, C–O–C and C–H/
C–C bonds from PLA, respectively [30]. Regarding the O 1s spectrum in
addition to the peaks for oxygen atoms participating in O–C_O and
C–O–C bonds at 533 and 532 eV, respectively, a peak at 530 еV was ob-
served as well. In accordance with the literature [31] it was attributed to
oxygen atoms engaged in Zn–O bond from ZnO structure.
The thermal stability of the new materials and the residual ZnO con-
tent was evaluated by TGA. The thermograms and their first derivatives
for PLA, EG10-on-PLA, ZnO-on-PLA, [ZnO/EG5]-on-PLA, [ZnO/EG10]-on-
188 D. Virovska et al. / Materials Science and Engineering C 60 (2016) 184–194
PLA and [ZnO/EG15]-on-PLA mats are presented in Fig. S1. EG and ZnO
powders were thermally stable in the studied temperature range —
from r.t. to 1000 °C no weight loss was detected. PLA mats degraded
at 340 °С. The presence of EG in EG5-on-PLA and EG10-on-PLA mats
did not significantly affect the degradation temperature and the detect-
ed one was at 349 °С. For ZnO-on-PLA mats, the presence of ZnO led to a
decrease in PLA thermal stability and PLA degradation occurred at 270
°C. This finding is in accord with data previously reported by us for
PLA/ZnO fibrous materials prepared by electrospinning or
electrospinning/electrospraying [22]. Degradation of the polymer at
lower temperature (ca. 260 °C) was also found for mats containing
both ZnO and EG: [ZnO/EG5]-on-PLA, [ZnO/EG10]-on-PLA and [ZnO/
EG15]-on-PLA. TGA enabled the determination of ZnO content in the
materials, and for ZnO-on-PLA, [ZnO/EG5]-on-PLA, [ZnO/EG10]-on-PLA
and [ZnO/EG15]-on-PLA mats it was 50%.
The glass transition temperature (Tg), cold crystallization tempera-
ture (Tcc), melting temperature (Tm), enthalpy of cold crystallization
(ΔHcc) and enthalpy of melting (ΔHm) of PLA, EG-on-PLA, ZnO-on-PLA
and [ZnO/EG]-on-PLA mats were determined by DSC. In the DSC ther-
mograms Tg, Tcc, and Tm for PLA were recorded at 63 °C, 85 °C and 167
°C, respectively. The determined ΔHcc and ΔHm values were 22.50 and
40.80 J/g, respectively. The occurrence of cold crystallization is in accord
with data for electrospun PLA materials and is attributed to the rapid
evaporation of the solvent during the electrospinning process thus
hampering the crystallization of the aliphatic polyester [32–36]. The cal-
culated crystallization degree of PLA in the electrospun mats was 20%.
Fig. 3. XRD patterns of ZnO and EG powders (A). XRD patterns of PLA, EG5-on-PLA, EG10-on-PLA and ZnO-on-PLA mats (B). Juxtaposition of the XRD patterns of [ZnO/EG5]-on-PLA (1),
[ZnO/EG10]-on-PLA (2) and [ZnO/EG15]-on-PLA (3) mats (C).
This crystallization degree value is consistent with our previous results
on the crystallization degree of PLA in electrospun PLA fibrous materials
prepared by electrospinning at a collector rotating rate of 1900 rpm
[36]. As expected, the presence of EG, ZnO or ZnO/EG in the mats did
not affect the thermal parameters and crystallinity degree of PLA as ev-
idenced by DSC.
The XRD patterns of PLA, EG-on-PLA, ZnO-on-PLA and [ZnO/EG]-on-
PLA mats recorded in 2θ range from 5 to 80° are presented in Fig. 3. For
comparison, the XRD patterns of ZnO and EG powder are given as well.
As seen from Fig. 3B and in accord with the data obtained by DSC on PLA
crystallinity degree of PLA mat, a broad peak with maximum at 2θ ca 17°
was observed thus indicating that PLA was in the amorphous state in
the fibers. Diffraction peaks at 2θ of 26.379°, 42.2° and 54° were detect-
ed in the XRD patterns of EG5-on-PLA and EG10-on-PLA mats (Fig. 3B).
They correspond to (002), (100) and (004) planes of EG flakes (JCPDS,
Card No. 75-1621) [37] (Fig. 3A) with a distance between the single
graphene layers of 0.337 nm. For ZnO-on-PLA fibrous material
(Fig. 3B) diffraction peaks characteristic for ZnO (Fig. 3A) at 31.8°,
34.5°, 36.4°, 47.6°, 56.6°, 62.8°, 66.3° and 68.1° were detected. They
are attributed to crystal planes of (100), (002), (101), (102), (110),
(103), (112) and (201) of hexagonal wurtzite ZnO with lattice constants
a = 0.325 nm and c = 0.521 nm (JCPDS, Card No. 75-0956) [38,39]. For
[ZnO/EG]-on-PLA fibrous materials diffraction peak characteristic for EG
and ZnO present in their XRD patterns (Fig. 3C). This indicated that the
new fibrous materials contained the both components of the ZnO/EG
hybrid.
 D. Virovska et al. / Materials Science and Engineering C 60 (2016) 184–194 189

The photocatalytic activity of the new self-cleaning materials was
evaluated in respect to Methylene Blue (MB) and Reactive Red (RR)
dyes under UV–vis irradiation. As seen from Fig. 4A, MB was sensitive
to UV–vis irradiation and for 3 h 25% of the dye degraded. In contrast,
the RR dye was much more stable than MB and its concentration did
not change during the 3-h UV–vis irradiation (Fig. 5A). It was found
that PLA and EG-on-PLA mats did not display any photocatalytic activity
— they did not alter the percentage of the degraded MB and did not lead
to RR degradation. In addition, this was an indication that no sorption of
the dyes by the fibrous materials occurred. The results obtained from
the photocatalytic degradation studies of MB under the action of ZnO-
on-PLA or [ZnO/EG]-on-PLA mats for three consecutive degradation cy-
cles are presented in Fig. 4A.
As seen from the first cycle of MB degradation, ZnO-on-PLA mats led
to 85% degradation of MB after a 180-min contact, and the dependence
of CMB/CMB
0 on UV–vis irradiation time is close to the linear one. 100% of
MB dye degraded under the action of [ZnO/EG]-on-PLA materials and
the time for complete MB degradation depended on EG content: 150,
120 and 90 min in the case of [ZnO/EG5]-on-PLA, [ZnO/EG10]-on-PLA
and [ZnO/EG15]-on-PLA mats, respectively. As seen from Fig. 4B, the ap-
parent rate constants (Kapp) of MB degradation for the first cycle in the
case of [ZnO/EG]-on-PLA mats were significantly higher than Kapp value
for ZnO-on-PLA mats.
Regarding the second and the third cycle Kapp values of the dye deg-
radation for ZnO-on-PLA mats were not significantly altered. However,
the percentage of non-degraded dye increased: from 15% in the first

Fig. 4. Reusability of mats in respect to MB degradation in three consecutive cycles: ZnO-on-PLA (■), [ZnO/EG5]-on-PLA (▲), [ZnO/EG10]-on-PLA (∇), [ZnO/EG15]-on-PLA (♦), and blank
control (□) (A). Kapp values of MB degradation (B).
190 D. Virovska et al. / Materials Science and Engineering C 60 (2016) 184–194
cycle to 25% in the third cycle (Fig. 4A). For [ZnO/EG5]-on-PLA mat a sig-
nificant delay of the photodegradation process was detected in the sec-
ond cycle: the determined Kapp value of MB degradation in the presence
of the mat decreased to 0.0052 ± 0.0004 min−1 (Fig. 4B). In addition,
MB did not completely degrade under the action of this mat for 3 h,
and the determined percentage of the non-degraded dye was 25%. The
[ZnO/EG10]-on-PLA and [ZnO/EG15]-on-PLA materials succeed in
completely degrading MB after 150 min in the second cycle and after
180 min in the third cycle, respectively. A decrease in the apparent
rate constant of the degradation process was detected as well
(Fig. 4B), and it was more pronounced in the case of [ZnO/EG10]-on-
PLA mat (comparing the first and second cycles of MB degradation).
The obtained results reveal that [ZnO/EG10]-on-PLA and [ZnO/EG15]-
on-PLA materials can be used repeatedly for MB photocatalytic degrada-
tion. Regarding the stable under UV–vis irradiation RR dye the obtained
data on its photocatalytic degradation under the action of ZnO-on-PLA
and [ZnO/EG]-on-PLA mats are presented in Fig. 5. Previously, we have
shown that RR is degraded more slowly by ZnO-on-PLA mats as com-
pared to MB [22]. This was ascribed to the presence of a triazine group
Fig. 5. Reusability in respect to RR degradation of mats: ZnO-on-PLA (■), [ZnO/EG5]-on-PLA (▲), [ZnO/EG10]-on-PLA (∇), [ZnO/EG15]-on-PLA (♦), and blank control (□) (A). Kapp values of
MB degradation (B).
in RR structure [40]. Here, it was also found that RR degraded more
slowly than MB. As seen in Fig. 5A, ZnO-on-PLA and [ZnO/EG5]-on-PLA
mats did not succeed in completely degrading the dye in the first degra-
dation cycle for 4 h. The non-degraded dye percentage was ca. 25 and
10%, respectively; and Kapp value of the degradation process was
lower than 0.01 min−1 (Fig. 5B). [ZnO/EG10]-on-PLA and [ZnO/EG15]-
on-PLA mats succeeded in completely degrading RR after 3 h during
the first cycle, and Kapp value (ca. 0.025 min−1) was significantly higher
than the calculated one for ZnO-on-PLA and [ZnO/EG5]-on-PLA mats. It
was found that only [ZnO/EG15]-on-PLA mats were able to completely
degrade RR during the second cycle. A decrease in Kapp value was de-
tected: from 0.025 min− 1 in the first to 0.015 min−1 in the second
cycle. The obtained results revealed that [ZnO/EG15]-on-PLA mats can
be used repeatedly for RR photocatalytic degradation. The enhancement
of the photocatalytic activity of [ZnO/EG10]-on-PLA and [ZnO/EG15]-
on-PLA materials as compared to ZnO-on-PLA mats may be attributed
to electron transfer from ZnO to EG in the ZnO/EG hybrid, which in
turn hampers the occurrence of the undesired process of recombination
of the electron–hole pairs in ZnO.
 D. Virovska et al. / Materials Science and Engineering C 60 (2016) 184–194 191

Fig. 6. A SEM micrograph of [ZnO/C600.5]-on-PLA mat (A, magnification: ×5000); and a TEM image of a single fiber from the same mat having aggregates from ZnO/C60 hybrid on its surface
(B, magnification: ×8000).

3.2. PLA/ZnO/C60 materials prepared by electrospinning/electrospraying

Toluene was selected to be one of the solvents in the mixed contin-

uous phase for preparation of the zinc oxide/C60 dispersion for the
electrospraying because of the solubility of C60 in this solvent. In order
to add a small amount of PLA: 0.05% (w/v), which served as a sticking
agent for the zinc oxide/C60 hybrid, we selected chloroform as the sec-
ond solvent. Our attempts to disperse zinc oxide with unmodified sur-
face in toluene or chloroform failed; presumably because of the
hydrophilicity of the zinc oxide. Thus, for the preparation of [ZnO/
C60]-on-PLA fibrous material nanosized zinc oxide with silanized surface
which is well-dispersible in both toluene and chloroform was used.
A SEM micrograph of [ZnO/C600.5]-on-PLA mat and a TEM image
of a single fiber from this material are shown in Fig. 6. The mats
were composed of cylindrical, defect-free fibers with mean diameter
of 1.70 ± 0.26 μm as well as of ZnO/C60 aggregates. The composition
of [ZnO/C60]-on-PLA surface was evaluated by XPS. In addition to car-
bon and oxygen, the presence of zinc (at 1023 eV) was detected as
well, thus evidencing that there was zinc oxide on the surface of
these mats. The determined zinc content on ZnO-on-PLA, [ZnO/
C 60 0.25]-on-PLA, [ZnO/C 600.5]-on-PLA, [ZnO/C 60 1.4]-on-PLA and
[ZnO/C602.5]-on-PLA mats surface was ca. 7%. The detailed C 1s spec-
tra of PLA, ZnO-on-PLA and [ZnO/C60]-on-PLA materials are given in
Fig. S2. For electrospun PLA mats, in accord with our previous data
[41] it was found that on their surface there are more carbon atoms
engaged in C–H/C–C bond than the theoretically calculated percent-
ages. Theoretically, the ratio between the peak areas of the corre-
sponding carbon atoms [C–/C–C]/[C–O–C]/[C_O] had to be 33.3/
33.3/33.3. The higher content of carbon atoms participating in C–H/
C–C bonds was attributed to enrichment of the fiber surface with car-
bon atoms with low binding energy owing to the applied voltage
during the electrospinning process. As expected, the presence of
ZnO in ZnO-on-PLA mats did not alter the [C–H/C–C]/[C–O–C]/
[C_O] ratio on their surface as compared to PLA mats. The presence
of C60 in [ZnO/C60]-on-PLA fibrous materials should lead to increase
in the area of the peak registered at 285 eV. At this binding energy
value in addition to carbon atoms participating in [C–H/C–C] bonds
(i.e., sp 3 -hybridized carbon atoms), sp2-hybridized carbon atoms
(like the carbon atoms in C 60 molecule) appear as well [42]. As
seen from Fig. S2, for [ZnO/C600.5]-on-PLA mat the area of the peak
at 285 eV was larger as compared to that for PLA or ZnO-on-PLA
mat. This indicated the presence of fullerene on the surface of
[ZnO/C600.5]-on-PLA materials. At higher fullerene content: [ZnO/
C601.4]-on-PLA and [ZnO/C602.5]-on-PLA mats, the area of the peak
at 285 eV additionally increased.
Fig. 7. Photocatalytic degradation of MB (A) and RR (B) in the presence of mats from: ZnO-
The zinc oxide content in the [ZnO/C60]-on-PLA mats determined by on-PLA (□), [ZnO/C600.25]-on-PLA (▼), [ZnO/C600.5]-on-PLA (○), [ZnO/C601.0]-on-PLA
TGA was 25%. The presence of zinc oxide in the mats led to a decrease in (Δ), [ZnO/C601.4]-on-PLA (♦), [ZnO/C602.0]-on-PLA (⋄), [ZnO/C602.5]-on-PLA (•); and
the degradation temperature of PLA. The recorded degradation blank control (▲).
192 D. Virovska et al. / Materials Science and Engineering C 60 (2016) 184–194
Fig. 8. Reusability in respect of MB degradation in three consecutive cycles under the ac-
tion of [ZnO/C600.5]-on-PLA mats.
temperature was 340 °C for PLA mats, while for ZnO-on-PLA mats that
contain 25% ZnO the detected one was 310 °C. The determined higher
temperature of PLA thermal degradation for ZnO-on-PLA mats with
25% ZnO (the control mats for the [ZnO/C60]-on-PLA series) as com-
pared to ZnO-on-PLA mats with 50% ZnO (the control mats for the
[ZnO/EG]-on-PLA series) can be attributed to the lower ZnO content of
the former mats. This result is in accord with data obtained for ZnO-
containing PLA materials prepared by extrusion [43]. The incorporation
of C60 in the mats did not affect the PLA degradation temperature and
the recorded values for [ZnO/C60]-on-PLA mats were similar to that for
ZnO-on-PLA mats. The performed DSC analyses revealed that the pres-
ence of ZnO or ZnO/C60 hybrid did not alter the PLA thermal character-
istics as well as the crystallinity degree (20%) of the polymer in the new
materials. In the XRD patterns of PLA, ZnO-on-PLA and [ZnO/C60]-on-
PLA mats in 2θ range from 10° to 25° only a broad amorphous halo
was detected thus evidencing that PLA was in the amorphous state in
the mats. It is known that C60 is crystalline and its characteristic diffrac-
tions are in 2θ range from 10° to 22° [44,45]. However, the recorded
broad amorphous halo for PLA in 2θ range from 10° to 25° did now
allow for the detection of C60 characteristic diffractions in the XRD pat-
terns of [ZnO/C60]-on-PLA mats. Regarding ZnO, all of the diffraction
characteristic for zinc oxide were detected in ZnO-on-PLA and [ZnO/
C60]-on-PLA materials.
The results from the photocatalytic degradation of MB and RR under
the action of [ZnO/C60]-on-PLA are presented in Fig. 7. As seen from
Fig. 7A, [ZnO/C600.5]-on-PLA mats had the best photocatalytic
Fig. 9. Agar plates of S. aureus bacterial suspensions incubated for 24 h: without contact with mats (A), and treated with [ZnO/C600.5]-on-PLA mats (B).
performance in respect to MB. In this case, complete MB degradation
was reached in 240 min. For [ZnO/C601.4]-on-PLA mats ca. 30% of the
dye remained non-degraded after a 240-min irradiation. The other
fullerene-containing materials exhibited photocatalytic activity compa-
rable with that of ZnO-on-PLA mats, and ca. 10% of MB was not degraded
after a 240-min irradiation. Regarding RR, the difference in the photo-
catalytic behavior of C60-containing mats was more pronounced. As
seen from Fig. 7B, ZnO-on-PLA, [ZnO/C600.5]-on-PLA and [ZnO/C602.5]-
on-PLA mats had similar photocatalytic activity, and after a 240-min ir-
radiation the amount of the non-degraded dye reached from 20% to 50%
under the action of ZnO-on-PLA or [ZnO/C602.5]-on-PLA materials,
respectively.
Again, like in the case of MB, [ZnO/C601.4]-on-PLA mats displayed
poor photocatalytic activity in respect to RR: using these fibrous mate-
rials just 5% of RR were degraded in 240 min. [ZnO/C600.5]-on-PLA and
[ZnO/C601.0]-on-PLA mats exhibited the best photocatalytic behavior
in respect to RR, and after a 240-min irradiation the non-degraded dye
was less than 10%. Kapp values of MB and RR degradation under the ac-
tion of ZnO-on-PLA and [ZnO/C60]-on-PLA mats are presented in Fig. S3.
[ZnO/C600.5]-on-PLA mats exhibited the strongest photocatalytic activ-
ity in respect to MB, and the calculated Kapp value was ca. 2-times higher
than Kapp value when ZnO-on-PLA mat was used for MB degradation.
For RR the highest Kapp values were calculated for the photocatalytic
degradation of the dye under the action of [ZnO/C600.5]-on-PLA and
[ZnO/C601.0]-on-PLA mats. As seen from Fig. S3B, for these materials
Kapp values of RR degradation were close in value and were almost 2-
times higher than Kapp of RR degradation in the presence of [ZnO]-on-
PLA. The detected enhanced photocatalytic activity in the case of
[ZnO/C600.5]-on-PLA and [ZnO/C601.0]-on-PLA mats provided evidence
that because of the electron transfer from ZnO to C60 the undesired pro-
cess of recombination of ZnO electron–hole pairs was significantly sup-
pressed at these values of fullerene content.
Since complete MB degradation was found when using [ZnO/
C600.5]-on-PLA mats, the latter were subjected to assessment of their re-
usability in terms of MB photocatalytic degradation. The obtained re-
sults are presented in Fig. 8. As seen, [ZnO/C600.5]-on-PLA fibrous
materials preserved their photocatalytic activity for at least three con-
secutive cycles of MB degradation, i.e. they can be used repeatedly for
degradation of this dye.
3.3. Microbiological assessment of the antibacterial activity of [ZnO/EG]-on-
PLA and [ZnO/C60]-on-PLA mats against S. aureus
[ZnO/EG]-on-PLA and [ZnO/C60]-on-PLA mats with the best photo-
catalytic performance: [ZnO/EG10]-on-PLA, [ZnO/EG15]-on-PLA, [ZnO/
C600.5] and [ZnO/C601.0], were subjected to microbiological tests in
order to evaluate their antibacterial potential against the pathogenic
 D. Virovska et al. / Materials Science and Engineering C 60 (2016) 184–194
Fig. 10. SEM micrographs of PLA (A) and [ZnO/EG15]-on-PLA (B) mats after 24-h contact with S. aureus suspension.
microorganism S. aureus. PLA and ZnO-on-PLA mats were used as con-
trols. An image of an agar plate of S. aureus bacterial suspension that
had not been in contact with a mat after a 24-h incubation at 6 dilutions
is given in Fig. 9A. The pathogenic microorganism developed and the
determined log(CFU/mL) was 8.65. It was found that the contact of
the bacterial suspension with PLA mats for 24 h did not inhibit
S. aureus growth and the log(CFU/mL) value was not altered, i.e. PLA
mats did not display any antibacterial activity.
S. aureus suspension was incubated for 24 h in the presence of [ZnO/
C600.5]-on-PLA mats. Agar plates were inoculated with the treated
suspension and incubated for 24 h. As seen (Fig. 9B) no S. aureus cell
colonies were observed, i.e. the mats manifested antibacterial activity.
The ZnO-on-PLA, [ZnO/EG10]-on-PLA, [ZnO/EG15]-on-PLA and [ZnO/
C601.0] mats also exhibited antibacterial activity against S. aureus.
The obtained data on the photocatalytic and antibacterial activity of
PLA fibers decorated with ZnO, ZnO/EG or ZnO/C60 clearly evidence the
self-cleaning potential of the new materials. They possess surface that is
contamination-free and self-disinfecting. To further confirm the
imparting of self-cleaning behavior to PLA mats by incorporation of
ZnO, ZnO/EG or ZnO/C60 SEM observations of the mats after their 24-h
contact with S. aureus suspension were conducted, as well. As seen
from Fig. 10A, PLA is a good substrate for S. aureus.
The pathogenic cells adhere very well on PLA fibers tending to form a
biofilm that is hazardous to human health. For ZnO-containing fibrous
materials no S. aureus cells are observed on the mat surface. For exam-
ple, as seen in Fig. 10B only EG flakes and ZnO aggregates exist in
[ZnO/EG15]-on-PLA mat after its 24-h contact with the suspension
of the pathogenic bacteria. Therefore, the utilization of the
electrospinning/electrospraying technique is a highly effective tool for
imparting self-cleaning behavior to PLA fibrous materials, thus broaden-
ing significantly the fields of application of PLA-based devices.
4. Conclusions
By applying the electrospinning in conjunction with electrospraying
the possibility for preparation of self-cleaning PLA fibers decorated with
ZnO/EG or ZnO/C60 hybrid was shown. The comparison of the photocat-
alytic behavior of [ZnO/EG]-on-PLA and ZnO-on-PLA mats in respect to
MB and RR revealed that the presence of EG enhanced the photoinduced
degradation activity of the mats. For the first cycle of MB and RR degra-
dation the photocatalytic activity of the mats followed the order: ZnO-
on-PLA b [ZnO/EG5]-on-PLA b [ZnO10-on-PLA] ≈ [ZnO/EG15]-on-PLA.
It was found that [ZnO/EG10-on-PLA] and [ZnO/EG15]-on-PLA could
be used repeatedly for degradation of MB dye, and [ZnO/EG15]-on-
PLA can be used repeatedly for degradation of RR dye. For [ZnO/C60]-
on-PLA mats it was shown that [ZnO/C600.5]-on-PLA and [ZnO/C601.0]-
on-PLA materials exhibited the strongest photocatalytic activity and
[ZnO/C600.5]-on-PLA could be used repeatedly for MB degradation.
193
The microbiological tests revealed that the new materials manifested
antibacterial activity against the pathogenic microorganism S. aureus.
Acknowledgments
The authors appreciate the contribution of Assoc. Prof. Dr. N. Marko-
va from the Institute of Microbiology, BAS in the performance of the mi-
crobiological tests.
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.msec.2015.11.029.
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