coatings

Article
Physico-Mechanical and Antibacterial Properties of
PLA/TiO2 Composite Materials Synthesized via
Electrospinning and Solution Casting Processes
Shiyi Feng 1,† , Feng Zhang 2,† , Saeed Ahmed 1 and Yaowen Liu 1,2,3, *
1 College of Food Science, Sichuan Agricultural University, Yaan 625014, China
2 School of Materials Science and Engineering, Southwest Jiaotong University, Chengdu 610031, China
3 California NanoSystems Institute, University of California, Los Angeles, CA 90095, USA
* Correspondence: lyw@my.swjtu.edu.cn
† These authors contributed equally to the work.




Received: 27 July 2019; Accepted: 15 August 2019; Published: 19 August 2019


Abstract: In this study, PLA/TiO2 composites materials were prepared via electrospinning and
solution casting processes. By testing the mechanical properties, water contact angle, water vapor
permeability, and solubility of the composite nanofibers and films, the comprehensive performances
of the two types of nanocomposites were analyzed. The results show that maximum tensile strengths
of 2.71 ± 0.11 MPa and 14.49 ± 0.13 MPa were achieved for the nanofibers and films at a TiO2
content of 0.75 wt.%. Moreover, the addition of TiO2 significantly cut down the water vapor
transmittance rate of the nanofibers and films while significantly improving the water solubility.
Further, the antibacterial activity increased under UV-A irradiation for a TiO2 nanoparticle content of
0.75 wt.%, and the nanofiber and films exhibited inhibition zones of 4.86 ± 0.50 and 3.69 ± 0.40 mm
for E. coli, and 5.98 ± 0.77 and 4.63 ± 0.45 mm for S. aureus, respectively. Overall, the performance of
the nanofiber was better than that of the film. Nevertheless, both the nanocomposite membranes
satisfied the requirements of food packaging materials.

Keywords: PLA; TiO2 ; nanofibers; films

1. Introduction
The widespread use of synthetic polymers has led to many environmental problems, primarily due
to their non-degradability. This phenomenon has stimulated interest in research on the production of
natural polymer-based biodegradable packaging systems. Bio-based and biodegradable polymers have
recently garnered attention as environmentally friendly alternatives to traditional plastic packaging
materials owing to their capacity to lessen the environmental impact. Polylactic acid (PLA) has good
biocompatibility, rigidness, and great thermoplastic for food packaging applications. However, PLA is
highly brittle and has poor gas and moisture barrier properties [1–3].
Titanium dioxide (TiO2 ) has been widely investigated over the past decade because of its
antimicrobial property caused by photocatalysis under light that generates enough energy for the
production of reactive oxygen species (ROS) such as •OH, H2 O2 , and O2 −•, which have the great
potential in damaging microbial cells [4]. Moreover, under the ultraviolet irradiation, the food-borne
microbes and allergens could be protected well [5]. Nanocomposite of composite TiO2 have been
comprehensively studied for different purposes such as amelioration in physical performances,
enhancement in the biodegradability of synthetic polymers, active packaging with antibacterial
activity for foodstuff, and degradation of organic pollutants. Alizadeh et al. prepared a whey protein
isolate/cellulose nanofiber with TiO2 and rosemary essential oil (REO) which might be a preservative

Coatings 2019, 9, 525; doi:10.3390/coatings9080525 www.mdpi.com/journal/coatings

Coatings 2019, 9, 525 2 of 17

for mutton microbes and sensory qualities. They found that the nanocomposite films containing TiO2
and REO inhibited the inhibit the growth of spoilage and pathogenic bacteria in meat, improved the
organoleptic properties of meat samples, and increased the longevity of meat samples [6]. Gumiero et
al. employed a blown film extrusion process to prepare a high-density polyethylene/calcium carbonate
film that contained TiO2 , and researched the influences of photocatalytic activity on the structural and
microbiological stability of a short-ripened cheese [7].
In recent years, much attention has been paid to PLA/TiO2 nanocomposites. PLA/TiO2
nanocomposites have good mechanical, thermal, and photocatalytic properties, and have potential
applications in the fields of adsorption and photocatalytic removal of environmental pollutants, food
preservation, coating materials, drug-controlled delivery systems, wound repair, and biosensors.
Toniatto et al. developed nanostructured PLA/TiO2 nanofibers by electrospinning. The nanostructured
PLA/TiO2 nanofibers presented no mammalian cell toxicity and, most importantly, possessed
bactericidal activity with larger TiO2 loadings [8]. Xing et al. investigated the effects on the antibacterial
and physical properties of polyethylene (PE)-based films after being loaded with nano-TiO2 particles;
their conclusions indicate that the TiO2 nanoparticles play the important role in antibacterial activity
of PE/TiO2 films [9]. Particularly, the microbicidal property of the PE/TiO2 composite film was more
impactful against S. aureus. Furthermore, they thought that this type of TiO2 -incorporated film might
sustain a high exchange of water molecules throughout the packaging system, which would prevent
high relative humidity within the packing, thus delaying fruit spoilage and increasing the shelf life of
fruits and vegetables with higher respiratory rates. Therefore, this type of film is a good candidate for
application as an active food packaging system [10].
In this study, PLA/TiO2 composite films and nanofibers with PLA as the film-forming substrate
and TiO2 as the functional substance were prepared by solution casting and electrospinning methods,
respectively. In the solution casting method, hybrid materials are prepared by direct dispersion
of nanoparticles in a polymer matrix. On the other hand, electrospinning is of interest for surface
coating of in situ generated nanoparticles specifically on the surface or in the bulk of a polymer matrix.
To determine the differences between the nanocomposite membranes prepared by the two methods for
application in antimicrobial packaging, the density, contact angle, water vapor permeability (WVP),
light transmittance, opacity, mechanical properties, and antibacterial activity of the nanocomposites
were studied to comprehensively analyze their practical application value.

2. Materials and Methods

2.1. Materials
An L-isomer consisting of 95.7% PLA was purchased from Nature Works LLC (Blair, NE, USA)
TiO2 nanoparticles (80% anatase and 20% rutile; diameter: 10 nm) were supplied by Evonik Degussa
GmbH (Essen, Germany). Chloroform and all the other solvents were of reagent grade or higher purity,
and were purchased from Chengdu Kelong Reagent Co. (Chengdu, China) unless otherwise indicated.

2.2. Electrospinning
A PLA solution (10%, w/w) was prepared by dissolving 1 g of PLA in a 10 mL co-solvent system
with a DCM-to-DMF ratio of 7:3 (v/v) under constant stirring at 800 rpm for 6 h. A certain amount
of TiO2 was added into the homogeneous PLA solution to form the PLA/TiO2 basic mixed solution.
The polymer solution was extracted using a 5 mL syringe with a blunt metal needle as the nozzle.
Control the distance between the collector and the tip to be maintained at around 15 cm, and a precision
pump (Zhejiang University Medical Instrument, Hangzhou, China) was used to set the flow rate as
1.0 mL/h. By using a high-voltage statitron (Tianjing High Voltage Power Supply Company, Tianjing,
China), the electrospinning voltage was controlled within 18 kV. A grounded roller collector was used
to collect the fibers. Before use, the overnight vacuum-dried need to be done at room temperature
of the fibers which aimed to eliminate any residual solution. The electrospun fibers were denoted as
Coatings 2019, 9, 525 3 of 17

PLA/TiO2 -1.5, PLA/TiO2 -1.25, PLA/TiO2 -1, PLA/TiO2 -0.75, and PLA/TiO2 -0.5, which correspond to
PLA-to-TiO2 weight ratios of 100:1.5, 100:1.25,100:1.0, 100:0.75, and 100:0.5, respectively.

2.3. Solution Casting

A certain amount of PLA particles was accurately weighed and dissolved in a chloroform solution,
and magnetically stirred at 40 ◦ C until complete dissolution into a transparent and uniformly viscous
solution. Then, 2 wt.% of Span 80 was added as a thickening agent, and a polylactic acid membrane
solution with 4 wt.% mass fraction was obtained. The same amounts of TiO2 were dissolved in 20 mL
of absolute ethanol to obtain five different nanocomposites with PLA-to-TiO2 weight ratios of 100:1.5,
100:1.25, 100:1.0, 100:0.75, and 100:0.5. After ultrasonic dispersion for 60 min, the mixture was slowly
added dropwise to the stirred PLA solution at a speed of two drops per second. After homogenization,
ultrasonic dispersion was carried out for 30 min to obtain a composite membrane solution. Then, 45 g
of different concentrations of the composite membrane liquid were respectively cast on glass plates
with dimensions of 24 cm × 24 cm, and dried in a vacuum oven at 55 ◦ C for 25 min to prepare the
composite membranes. Finally, the membranes were dried in air for 48 h until the chloroform solvent
in the composite membrane was sufficiently volatilized and PLA/TiO2 nanocomposite membranes of
different mass concentrations were obtained.

2.4. Morphological Characterization

The morphologies of the nanofibers and films were observed using a high-resolution scanning
electron microscope (SEM; Su 66000, Hitachi, Japan) operating at an accelerating voltage of 20 kV.
The sample was cut into 2 × 2 mm2 small pieces and fixed on a clean circular metal tray. Then a
thin layer of gold was evenly sprayed onto the surface of the film under vacuum conditions. Finally,
the morphology of the samples was observed under the SEM. The TiO2 nanoparticles incorporated
into PLA were subjected to transmission electron microscopy (TEM; JEM-2010 HR-TEM, JEOL, Tokyo,
Japan) for morphological analysis.

2.5. Film Density Measurement

A thickness meter was used to measure the thicknesses of five regions of the sample film: the four
corners and the center on the sample film. The weight m was measure using an analytical balance,
and the measured length and width were l and d, respectively. The density (ρ) was measured three
times were parallel measured by the samples in each group and calculated by the following formula:

ρ = m/l·d·a (1)

2.6. FTIR Analysis

Fourier transform infrared (FTIR) analysis was performed to investigate the interactions between
the main components of the film-forming materials. The film samples were characterized by FTIR
spectroscopy (FTIR-650, Suzhou Leiden Scientific Instrument Co., Ltd., Suzhou, China) at 23 ◦ C and
62.3% RH. The spectra in the range of 4000–650 cm−1 with automatic signal gain was collected in
32 scans at 4 cm−1 spectral resolution. To fully illustrate the result, each film sample was measured at
three stochastic locations.

2.7. Tensile Properties

The tensile strength (TS) and elongation at break (EB; in percentage) of the nanofibers were
measured using a texture analyzer (TA xT plus 50, Stable Micro Systems Ltd., Vienna, UK). Film
staples (60 mm × 10 mm) were cut into a uniform size and followed the settings to test the tensile
properties: pre-test speed of 20 mm/s, test speed of 3 mm/s, post-test speed of 10 mm/s, distance of
50 mm, and trigger force of 10 g, with the probe attached to a 5 kg load cell. Before the test, the samples
were placed in a 50% RH chamber at 23 ◦ C for 48 h.
Coatings 2019, 9, 525 4 of 17

2.8. Measurement of Water Solubility

The water solubility of the sample films was measured by employing the method recommended in
ref. [11]. The film samples were cut into 2 cm × 2 cm rectangles, dried at 105 ◦ C for 24 h, and the initial
dry weight (W i ) was measured. Then put them into 50 mL of distilled water at 25 ◦ C and agitated for
24 h, filter the solutions through a Whatman No. 1 filter paper. Next, dry the papers in a forced-air
oven (105 ◦ C, 24 h) and measured the final dry weight (W f ). The film solubility (%) was calculated by
the following formula:
Solubility (%) = (W i − W f ) × 100/W i (2)

2.9. WVP Measurement

The WVP of the bilayer films was gravimetrically determined according to previous reported [12].
Cut the films into a certain size and seal them on the top of a glass permeation cell (internal
diameter = 3 cm). Use the silica gel to preserve the desiccator at 20 ◦ C and 1.5% RH (28.044 Pa water
vapor pressure) which made the cell involved distilled water (100% RH; 2.337 × 103 Pa vapor pressure
at 20 ◦ C) and stir the air in the desiccators. To determine the permeated weight loss of cell, the sample
films were mensurated at intervals of 48 h for 10 days. This part of the water adsorbed by the desiccant
was regarded as water that permeates out of the film, and could also be considered as a loss of cell
weight. The slope of the functional relationship between the weight loss and the time curve is obtained
by a linear regression equation. The WVP was calculated by the following formula:

WVP = (C·X/A·∆P) (3)

where C is the transmission rate of water vapor (gls), X is the mean film thickness (mm), A is the area
of exposed film (mm2 ), and ∆P is the partial water vapor pressure difference (Pa) between the both
sides of the film. Repeat three tests for each sample to determine repeatability.

2.10. Contact Angle Measurement

A sessile drop assay was performed to measure the water contact angle on the samples by optical
contact angle measurement. A water droplet (~20 µL) was gently deposited onto the surface of the
nanofiber films, and photographs of the film surface were taken 5 s after droplet deposition. The angle
between the water droplet and the surface of the film was confirmed by Image J software (version
Java 1.6.0_05).

2.11. Light Transmittance and Opacity Measurements

The UV-vis transmission spectra of the film specimens were recorded in the range of 200~800 nm
using a UV-vis spectrophotometer (UV-1800 (PC), Shanghai AuCy Instrument Co. Ltd., Shanghai,
China). The opacity of the film specimens with well-controlled thicknesses that were put in the
spectrophotometer test cell was calculated by the following formula [13]:

Opacity = Abs600/X (4)

where Abs600 is the absorbance at 600 nm, and X is the film thickness (mm). Convert the absorbance
values to transmittance values using the Lambert-Beer equation. The measurement was repeated at
least three times.

2.12. Antimicrobial Test

The antibacterial performance of the composite membrane against Escherichia coli (E. coli) and
Staphylococcus aureus (S. aureus) were investigated by the inhibition zone method [14]. The film
specimens were cut into small pieces of 10 mm diameter and irradiated for 48 h under UV-A light
before fully activating the photocatalytic properties of TiO2 . The light source of UV radialization was
Coatings 2019, 9, 525 5 of 17

an 8 W Philip Cleo fluorescent lamp (Philips Co., Amsterdam, Holland) operating at its maximum
intensity at 360 nm (i.e., the UV-A region) for 6 h. The vertical distance of illumination was 10 cm.
Moreover, to verify the effects of the light source on the antibacterial ability of TiO2 , the experiment
was respectively carried out under ultraviolet light irradiation and non-irradiation conditions. The UV
irradiation of PLA/TiO2 nanofibers was actualized in a CTC 256 climate chamber (Memmert (Shanghai)
Trading Co., Ltd., Shanghai, China) maintained at 25 ◦ C and a relative humidity of 70%. In order to
have a certain amount of water molecules on the surface of TiO2 , the environment needed to maintain
a high relative humidity. The bacteria were placed in a solid incubator at 37 ◦ C and inoculated for
24 h to allow the bacteria to enter a stable log phase. After the test bacteria were activated, three
gradients were diluted with physiological saline, and then 100 µL of microbial cell suspension having
a concentration of 10−3 –10−4 (105 –106 CFU/mL) was uniformly spread on the surface of the solid
medium with an applicator until the surface dried. Then, a disc membrane was placed in the middle
of the substrate. Finally, the medium was cultured in a constant-temperature incubator for 48 h
at 37 ◦ C. The bacteriostatic effect was estimated by measuring the diameter of the inhibition zone.
The measurement was repeated at least three times.

3. Results and Discussions

3.1. Morphological Characteristics of PLA/TiO2 Nanofibers and PLA/TiO2 Films

Figure 1 shows that the nanofibers have a dimeter of 500–900 nm, which increased with the
accretion of nano-TiO2 particles. Figure 2 shows the morphology of the PLA/TiO2 films. As can be
seen, the surface roughness increased with an increase in TiO2 nanoparticle content. Besides, with
an increase in the concentration of TiO2 nanoparticles, their dispersibility decrease, thereby inducing
agglomeration of nanoparticles. PLA/TiO2 nanofibers exhibited a good appearance when combined
with nano-TiO2 at a concentration of 1.25 wt.% or less. However, when the concentration reached
1.50 wt.%, the characteristic fiber morphology was significantly changed owning to the loading of
nano-TiO2 . For the PLA/TiO2 nanocomposite film, the smooth surface characteristic feature of the film
changed when nano-TiO2 with a concentration of 1.0 or higher was loaded. The same phenomenon
was observed in the experiment carried out by Xie et al. [9]. They found that incorporated nano-TiO2
with PCL could form the porous structure and accumulation of TiO2 nanoparticles which result in
the uneven surface. Nevertheless, the PLA matrix acted as a good stabilizing agent for the TiO2
nanoparticles, as indicated by the spherical discrete particles in the SEM images of both PLA/TiO2
nanofibers and films.
The TEM images show the TiO2 nanoparticles and their uniform distribution on the PLA fibers
and films. The TiO2 nanoparticles are spherical with a uniform morphology. Among the all composite
fibers and films with different concentrations of TiO2 , the PLA/TiO2 -0.75 nanofibers and films showed
the best dispersion of TiO2 nanoparticles (Figure 3). The nano-TiO2 nanoparticles which were more
uniformly dispersed in the nanofibers and the nanocomposite films exhibited a good mosaicism,
and did not affect the normal morphology of the nanofibers and the nanocomposite membranes while
functioning. In addition, the particle size, estimated from the selected area electron diffraction pattern,
was found to be 10–20 nm, which was verified by light transmittance and opacity data. The similar
result was reported by Toniatto et al. who discovered that through the electrospinning progress,
a homogeneous distribution of nano-TiO2 enabled with PLA was formed [8].
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Figure
1. 1. SEMimages
images of polylactic
polylactic acid
acid(PLA)/TiO 2 nanofibers: (a) pure PLA; (b) PLA/TiO2-0.5; (c)
Figure
Figure 1.SEM
SEM images of of polylactic acid (PLA)/TiO
(PLA)/TiO 2 nanofibers:
2 nanofibers: (a) pure
(a) pure PLA;PLA; (b) PLA/TiO
(b) PLA/TiO 2-0.5; 2 -0.5;
(c)
PLA/TiO
(c) PLA/TiO 2-0.75; (d) PLA/TiO2-1.0; (e) PLA/TiO2-1.25, and (f) PLA/TiO2-1.5.
PLA/TiO22-0.75;
-0.75;(d)
(d)PLA/TiO
PLA/TiO 2 -1.0;
2-1.0; (e)(e) PLA/TiO
PLA/TiO 2 -1.25,
2-1.25, andand (f) PLA/TiO
(f) PLA/TiO 2 -1.5.
2-1.5.

Figure 2. 2.SEM
Figure SEM images
images of PLA/TiO
PLA/TiO2 films:
films:(a)(a) pure
pure PLA;PLA;
(b) (b) PLA/TiO
PLA/TiO 2-0.5; -0.5; (c) PLA/TiO
(c) PLA/TiO -0.75;
2-0.75; (d)
Figure 2. SEM images of PLA/TiO22 films: (a) pure PLA; (b) PLA/TiO2-0.5;2 (c) PLA/TiO2-0.75;2(d)
(d)PLA/TiO
PLA/TiO2-1.0;
2 -1.0; (e) PLA/TiO -1.25,
(e) PLA/TiO2-1.25,
2 and (f) PLA/TiO
and (f) PLA/TiO2-1.5.2 -1.5.
PLA/TiO2-1.0; (e) PLA/TiO2-1.25, and (f) PLA/TiO2-1.5.
Coatings 2019, 9, 525 7 of 17
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Figure 3. TEM images of (a) PLA/TiO22-0.75 nanofiber and (b) PLA/TiO

PLA/TiO22-0.75 film.

3.2. Film Density

3.2. Film Density
The density of
The density of the
the nanofibers
nanofibers andand films
films with
with different
different TiOTiO22 contents
contents are
are displayed
displayed in in Table
Table 1.
1.
Both
Both the
the PLA/TiO nanofibers and
PLA/TiO22 nanofibers and films
films were
were thicker
thicker than
than the
the control
control film;
film; however,
however, there
there waswas no
no
significant difference in their thicknesses (p > 0.05). Due to the addition of nanosized
significant difference in their thicknesses (P > 0.05). Due to the addition of nanosized TiO2 particles TiO 2 particles
into the PLA
into the PLA matrix
matrix with
with aa dense
dense chemical
chemical structure,
structure, the
the internal
internal space
space network
network structure
structure ofof the
the PLA
PLA
polymer
polymer waswas destroyed,
destroyed,causing
causingan anoverall
overalldensity
densityreduction
reduction [15].
[15]. A similar
A similar result
result waswas presented
presented for
for whey protein isolate films containing porous silica-coated nano-TiO particles
whey protein isolate films containing porous silica-coated nano-TiO2 2particles as a reinforcing as a reinforcing
medium
medium [16]. Nevertheless, the
[16]. Nevertheless, the density
density of
of the
the PLA/TiO
PLA/TiO22-1.25-1.25 nanofibers
nanofibers and
and films
films increased
increased slightly;
slightly;
this
this is
is possibly
possibly because
because of
of the
the increase
increase in
in the
the amount
amount of of added
added TiO
TiO22,, which
which isis difficult
difficult to
to disperse
disperse
and
and likely to agglomerate in PLA, resulting in a slightly increased density than that of thethe
likely to agglomerate in PLA, resulting in a slightly increased density than that of former.
former. A
A similar result was obtained by the addition of TiO 2 nanoparticles and high-pressure
similar result was obtained by the addition of TiO2 nanoparticles and high-pressure hydrodynamics hydrodynamics
to
to improve
improve thethe functions
functions of
of aa PVA/CS
PVA/CScomposite
compositefilm film[17].
[17].
Furthermore, the density of the nanofibers was lower than that of the films, which could be
Table 1. Density of PLA/TiO2 nanofibers and films with different contents of TiO2 .
ascribed to the small average size of TiO2 nanoparticles distributed on the PLA nanofibers. Even
though tens of thousands of fibers
Sample/Density were
(g/cm3 ) interwoven to form the nanofiber, theFilm
Nanofiber resulting network was
porous due to the pores between
PURE PLA the fibers, which0.98 reduced
± 0.03 athe density as1.01
compared
± 0.04 b with that of the
films. On the contrary, the film
PLA/TiO 2 -0.5was cast from a mixture
0.64 ± of
0.08 PLA
b solution and
0.73 TiO
± 2 dispersion
0.03 a liquid.
c b molecules; as a
The intermolecular PLA/TiO
crosslinking
2 -0.75 was strong, and the
0.30 ±pores
0.07 were occupied
0.33by
± PLA
0.01
result, the films were PLA/TiO 2 -1 the nanofibers. 0.28 ± 0.04
denser than
d 0.27 ± 0.01 c
PLA/TiO2 -1.25 0.36 ± 0.03 c 0.43 ± 0.02 a
PLA/TiO -1.5 0.39 ± 0.09 b 0.55 ± 0.03 d
Table 1. Density 2of PLA/TiO2 nanofibers and films with different contents of TiO2.
a, b, c, d: Means with different letters within a column indicate significant differences (p ≤ 0.05).
Sample/Density(g/cm3) Nanofiber Film
PURE of
Furthermore, the density PLAthe nanofibers was lower 0.98 ± 0.03a
than 1.01
that of the films, ± 0.04b
which could be ascribed
to the small average sizePLA/TiO
of TiO22-0.5 0.64on
nanoparticles distributed ± 0.08b 0.73 ±Even
the PLA nanofibers. 0.03athough tens of
thousands of fibers werePLA/TiO 2-0.75 to form the nanofiber,
interwoven 0.30the
± 0.07c
resulting network0.33was
± 0.01b
porous due to the
pores between the fibers, which reduced
PLA/TiO 2-1 the density as compared
0.28 ± 0.04d with that of the
0.27films. On the contrary,
± 0.01c
the film was cast from a mixture
PLA/TiO of PLA solution and
2-1.25 TiO
0.36 dispersion liquid.
± 20.03c 0.43 ±The intermolecular
0.02a
crosslinking was strong, and the
PLA/TiO2-1.5 pores were occupied by PLA
0.39 ± 0.09bmolecules; as
0.55 ± 0.03dthe films were
a result,
denser a,
than
b, c,the nanofibers.
d: Means with different letters within a column indicate significant differences (P ≤ 0.05).

3.3. Contact Angle

3.3. Contact Angle
The water contact
The water contact angles
anglesof
ofthethePLA/TiO
PLA/TiO2 2nanofibers
nanofibersandandfilms
films are
are shown
shown in in Figure
Figure 4. As
4. As cancanbe
be seen,
seen, both
both PLA/TiO
PLA/TiO 2 nanofibers
2 nanofibers andandfilmsfilms
showshow the same
the same trendtrend of change
of change in water
in water contact
contact angle.angle.
The
◦ ◦
The
waterwater contact
contact angleangle
of 138.4° ± 5.2°±of5.2
of 138.4 theof thefibers
PLA PLA fibers
is dueistodue
the to the hydrophobicity
hydrophobicity of thefibers,
of the PLA PLA
fibers,
which is which is evident
evident from the from the appearance
appearance of spherical
of spherical water droplets
water droplets on the on thesurface
fiber fiber surface for
for a long
a long period. The water contact angle of the PLA film (113.5 ◦ ± 2.7◦ ) was slightly lower than
period. The water contact angle of the PLA film (113.5° ± 2.7°) was slightly lower than that of the
that
PLA of the PLA
fibers. Thisfibers. This isbecause
is probably probablythe because the filmwas
film surface surface was smoother
smoother than the than the nanofiber
nanofiber surface,
surface,
which led to its greater interaction with water, thereby resulting in a smaller water contactcontact
which led to its greater interaction with water, thereby resulting in a smaller water angle.
The water contact angles of the nanofiber and film slightly decreased due to the addition of 0.75
wt.% TiO2 (122.1° ± 6.2° and 98.7° ± 4.4°, respectively). The water contact angle decreases with
Coatings 2019, 9, 525 8 of 17

angle. 2019,
Coatings The 9,
water
x FORcontact angles
PEER REVIEW of the nanofiber and film slightly decreased due to the addition 8 of of
17
0.75 wt.% TiO2 (122.1◦ ± 6.2◦ and 98.7◦ ± 4.4◦ , respectively). The water contact angle decreases with
incremental
incremental surface
surface hydrophilicity.
hydrophilicity. Considering
Considering this, this, the
the reduced
reduced contact
contact angle
angle measured
measured in in this
this
study
study maymay be
be attributed
attributed to to the
the lower
lower hydrophilicity
hydrophilicity of of TiO
TiO22,, which
which might
might result
result in in the
the augment
augment of of
surface
surface hydrophilicity.
hydrophilicity. Zhang Zhang et et al.
al. also
alsoreported
reported thatthat the
the contact
contact angle
angle decreases
decreases because
because of of the
the
hydrophilic
hydrophilic nature
nature of of the
the incorporated
incorporated TiO TiO22 nanoparticles,
nanoparticles, which which resulted
resulted in in significantly
significantly enhanced
enhanced
hydrophilicity
hydrophilicity [18].
[18]. Alternatively,
Alternatively, the the decrease
decrease in in contact
contact angle
angle upon
upon addition
addition of TiO22 nanoparticles
of TiO nanoparticles
can
can be
be attributed
attributed to
to the
the increases
increases in in surface
surface free
free energy
energy andand surface
surface roughness
roughness of of the
the film.
film. However,
However,
the contact angle of the nanofibers increased to 143.4°
◦ ± 4°,
◦ while that of the
the contact angle of the nanofibers increased to 143.4 ± 4 , while that of the films slightly increased films slightly increased to
to 119.1°
119.1 ◦ ±5±◦5° witha afurther
with furtherincrease
increaseininthetheTiOTiO2
content
2content to
to 1.25
1.25 wt.%.
wt.%. However,
However, beyond
beyond 1.25
1.25 wt.%
wt.% of
of
TiO
TiO22,, no
no significant
significant difference
difference waswas observed
observed in the water
in the water contact
contact angles.
angles. ThisThis is is because
because increasing
increasing
the
the amount
amount of of TiO
TiO22 nanoparticles
nanoparticles results
results inin particle
particle agglomeration
agglomeration in in the
the film,
film, which
which increases
increases thethe
hydrophobicity
hydrophobicity of ofthethefilm.
film. Salarbashi
Salarbashi et [19]
et al. al. [19] claimed
claimed that combined
that combined the TiOthe 2
TiO
with 2 with soybean
soluble soluble
soybean polysaccharide
polysaccharide could increase could increase hydrophobicity
hydrophobicity of bionanocomposite of bionanocomposite film which also
film which also authenticated our
authenticated
results. Similarour results.
findings Similar
were findings
reported were reported
by Alippilakkotte et by Alippilakkotte
al. [20]. Moreover, some et al. papers
[20]. Moreover,
reported
some papers
that owing toreported that owing
the increased surfacetohydrophobicity,
the increased surface
accreting hydrophobicity,
the amount of TiO accreting the amount of
2 nanoparticles tends
TiO nanoparticles tends to prevent the water drop from
to prevent the water drop from spreading over the film surface [21,22].
2 spreading over the film surface [21,22].

Figure 4. Variation in water contact angle with the addition of TiO2 nanoparticles in (a) PLA nanofibers
Figure 4. Variation in water contact angle with the addition of TiO2 nanoparticles in (a) PLA
and (b) PLA films. Columns with * mean significantly different (p ≤ 0.05).
nanofibers and (b) PLA films.
3.4. FTIR Study
3.4. FTIR Study
The molecular interaction between the raw materials and TiO2 nanoparticles was studied by
The molecular
Fourier transform interaction
infrared between(FTIR).
spectroscopy the raw Asmaterials
there wasand TiO2 nanoparticles
no difference was studied
in the functional groupsby of
Fourier transform
the nanofiber and film, infrared spectroscopy
as observed (FTIR).
by FTIR analyses,As there
a purewas
PLA nofiber
difference in the functional
and a PLA/TiO 2 film weregroups
used
of
as the nanofiber and
representatives forfilm, as observed
drawing. The FTIR byspectra
FTIR analyses, a pure PLA fiber
of TiO2 nanoparticles, pure and
PLA a PLA/TiO
fiber, and2 film were2
PLA/TiO
used as representatives for drawing. The FTIR spectra of TiO
film are shown in Figure 5. The TiO2 spectrum shows weak peaks around 1630 cm and 3440 cm 2 nanoparticles, pure −1 PLA fiber, and−1 ,
PLA/TiO
which arise 2 film
fromare theshown in Figure
stretching 5. The
vibrations of TiO 2 spectrum
surface shows
O–H groups of weak peaks
TiO2 [23]. Inaround
addition, 1630
the cm –1 and
vibration
3440 cm −1, which −1 arise from the stretching vibrations of surface O–H groups
band at 1110 cm originates from the stretching of C–O–C bonds [24]. In the pure PLA fiber spectrum, of TiO 2 [23]. In addition,
the
the vibration
weaker peak band at at 1110
2925 cmcm−1 –1 originates
appears due from
to thethe stretchingstretching
asymmetric of C–O–Cvibrations
bonds [24]. of In
–CHthe3 and
pure–CHPLA2 ,
fiber spectrum, peak
the absorption the weakerat 1750peak
cm atarises
−1 2925 cm
fromappears
−1 due to vibration
the stretching the asymmetric stretching
of aldehyde vibrations
or ester carbonyl of
–CH 3 and –CH 2 , the absorption peak
−1 at 1750 cm –1 arises from the stretching vibration of aldehyde or
C=O [25], and the peak at 1080 cm arises from the stretching vibrations of C–O–C bonds and C–O
ester
bondscarbonyl
[26]. In theC=O [25], and
spectrum the PLA/TiO
of the peak at 1080 cm−1 arises from the stretching
2 film, the band at around 3420 cm
−1 isvibrations
caused by of theC–O–C
tensile
bonds and C–O bonds [26]. In the spectrum of the PLA/TiO film, the
vibration of the characteristic hydroxyl group of TiO2 nanoparticles, and shows a slight shift from
2 band at around 3420 cm −1 is

caused
3440 cmby −1 .the tensile
This vibration
is possibly of thethe
because characteristic
mixing of PLA hydroxyl
with TiOgroup of TiO2 nanoparticles, and shows
2 led to partial incorporation of a large
aamount
slight shift from 3440
of hydroxyl groupscm present
−1 . This is
onpossibly
the TiO2 because the the
surface into mixing of PLA
composite with TiO2resulting
membrane, led to partial
in the
incorporation of a large amount of hydroxyl groups present on the TiO
appearance of the vibration peak of hydroxyl group in the composite membrane spectrum. In addition, 2 surface into the composite
membrane, resulting in the appearance of the vibration peak of hydroxyl group in the composite
membrane spectrum. In addition, the peak at 2925 cm−1 arising from the vibrations of –CH3 and
–CH2 of pure PLA film shifted to 2930 cm−1. The addition of nanoparticles kept the signal at 1750 and
1080 cm–1 unchanged, which might probably due to the physical mixing of PLA and TiO2. However,
Coatings 2019, 9, 525 9 of 17

the peak at 9,2925 cm −1

Coatings 2019, x FOR PEERarising
REVIEWfrom the vibrations of –CH3 and –CH2 of pure PLA film shifted 9 of to
17
2930 cm . The addition of nanoparticles kept the signal at 1750 and 1080 cm−1 unchanged, which
−1

might probably
the intensity due to the physical
of absorption peak andmixing
the areaofunder
PLA andthe TiO
peak 2 . increased
However,forthethe
intensity
PLA/TiO of 2absorption
specimens
peak and the
compared withareathe
under
pure thePLA
peakfiber.
increased
Li et for
al. the PLA/TiO
observed specimens
a 2similar compared
increase in peakwith the pure PLA
intensities [27].
fiber. Li et al. observed a similar increase in peak intensities [27]. Overall, no new
Overall, no new peaks were detected for the PLA/TiO2 nanocomposite films, which indicated that peaks were detected
for the PLA/TiO
except 2 nanocomposite
for the surface hydroxyl groupfilms,present
which on indicated
the TiOthat except for the
2 nanoparticles, thesurface hydroxyl
components weregroup
only
present on the
physically TiO2Besides,
mixed. nanoparticles, the components
no functional were only
group changes physically
occurred, mixed.
and the baseBesides, nooffunctional
structure the films
group
was not changes occurred, and the base structure of the films was not destroyed.
destroyed.

Figure 5. FTIR
Figure 5. FTIRspectra
spectraofofTiO2 nanoparticles,
TiO pure PLA, PLA/TiO2 -0.75
2 nanoparticles, pure PLA, PLA/TiO
nanofiber, and PLA/TiO2 -0.752film.
2-0.75 nanofiber, and PLA/TiO -0.75
film.
3.5. Water Solubility
As shown
3.5. Water in Table 2, the solubility of the nanofibers and nanocomposite films significantly
Solubility
increased as the TiO2 content increased from 0 to 1.0 wt.%. Owning to the hydrophilicity of nano-TiO2 ,
As shown
the water in Table
solubility of the2,nanocomposite
the solubility ofwasthehigher
nanofibers andofnanocomposite
than that the hydrophobic films
puresignificantly
PLA film.
increased as
However, as the
the TiO
TiO2 content
content ofincreased from 0 to 1.0
the nanocomposite wt.%.
films was Owning
increasedtotothe
1.25hydrophilicity
and 1.50 wt.%, of
2
nano-TiO 2, the water solubility of the nanocomposite was higher than that of the hydrophobic pure
the solubility of the films significantly decreased (p < 0.05). This trend can be accounted for the
PLA film.
higher However, of
concentration as TiO
the TiO 2 content of the nanocomposite films was increased to 1.25 and 1.50
2 nanoparticles (1 wt.%), which reduced the space available to host water
wt.%, the solubility
molecules, of the
and/or result infilms significantly
the stronger decreased
interactions (P < 0.05).
between This trend
nano-TiO can be accounted for the
2 particles and PLA that led to
higher concentration of TiO2 nanoparticles (1 wt.%), which reduced the space available to host water
the TiO2 particles acting as a crosslinker, thereby arresting water access [28,29]. A parallel observation
molecules, and/or result in the stronger interactions between nano-TiO2 particles and PLA that led to
was reported by Alizadeh-Sania, who demonstrated that high levels of film swelling by water inhibit
the TiO2 particles acting as a crosslinker, thereby arresting water access [28,29]. A parallel
their biodegradability. Besides, it could be observed that the solubility of nanofibers was higher than
observation was reported by Alizadeh-Sania, who demonstrated that high levels of film swelling by
that of the nanocomposite films, which is probably because electrospinning led to uniform spinning
water inhibit their biodegradability. Besides, it could be observed that the solubility of nanofibers
of the nanofibers, which could fully distribute the nanosized TiO2 [30]. On the contrary, during the
was higher than that of the nanocomposite films, which is probably because electrospinning led to
solution casting process, TiO2 nanoparticles were more likely to aggregate, which reduced the specific
uniform spinning of the nanofibers, which could fully distribute the nanosized TiO2 [30]. On the
surface area of TiO2 as compared with that of the nanofibers; hence, its hydrophilicity could not give
contrary, during the solution casting process, TiO2 nanoparticles were more likely to aggregate,
full play to the effect [31].
which reduced the specific surface area of TiO2 as compared with that of the nanofibers; hence, its
hydrophilicity could
Table not give
2. Density offull play2tonanofibers
PLA/TiO the effectand
[31].
films with different contents of TiO2 .

Sample/Water Solubility
Table 2. Density (%)2 nanofibers Nanofiber
of PLA/TiO Filmof TiO2.
and films with different contents
PURE PLA 1.12 ± 0.3 a 1.08 ± 0.2 b
Sample/Water
PLA/TiO2 -0.5solubility (%) Nanofiber
9.57 ± 0.8 b
Film
4.82 ± 0.4 a
PURE
PLA/TiO 2 -0.75PLA 15.63 ± 0.71.12 ± 0.3a
c
9.46 1.08
± 0.6± 0.2b
b

PLA/TiO
PLA/TiO2 -1 2-0.5 34.09 ± 1.4 d
9.57 ± 0.8b ± 0.9± c0.4a
19.294.82
PLA/TiO2 -1.25 16.87 ± 1.3 c 10.14 ± 0.3 a
PLA/TiO2-0.75 15.63
b
± 0.7c 9.46 ± 0.6b
PLA/TiO2 -1.5 8.80 ± 0.9 5.05 ± 0.2 d
PLA/TiO2-1 34.09 ± 1.4d 19.29 ± 0.9c
a, b, c, d: Means with different letters within a column indicate significant differences (p ≤ 0.05).
PLA/TiO2-1.25 16.87 ± 1.3c 10.14 ± 0.3a
PLA/TiO2-1.5 8.80 ± 0.9b 5.05 ± 0.2d
a, b, c, d: Means with different letters within a column indicate significant differences (P ≤ 0.05).

3.6. Water Vapor Permeability

WVP of the PLA/TiO2 nanofibers and films exhibited the same trend and decreased significantly with
an enhancive content of TiO2 from 0 to 1 wt.%. However, further increasing the TiO2 content increased
the WVP of the nanofibers and films. This is because the hydrophobic TiO2 nanoparticles prevented
the micro- and nano-paths in the network structure [32]. At low contents, the nano-TiO2 particles
could
Coatingsproperly separate throughout the matrix, thereby blocking the entry of water vapor. The reason
2019, 9, 525 10 of 17
why WVP appears to drop significantly after adding nanoparticles could be primarily attributed to
the highly complex path that was generated because of the distribution of impermeable TiO2
3.6. Water Vapor Permeability
nanoparticles throughout the matrix. Generally, the nanoparticles increase the pass length of water
Figureby
molecules 6 shows the effects
compelling the ofpermeating
nanoparticlemolecules
content ontotherandomly
WVP of the nanofibers
oscillate and films.
around them The [33].WVPAs
of the PLA/TiO
previously mentioned,
2 nanofibers
the and
number filmsof exhibited
available the
OH same
groupstrend and
reduced decreased
because significantly
of the production with an
of
enhancivebonds
hydrogen content of TiO2Ti–O
between fromand 0 tothe1 wt.%.
hydroxylHowever,
groupsfurther
of PLA;increasing the TiO2 reduced
this consequently content increased
the WVP
thethe
of WVP of the
films. nanofibers
Moreover, and films. This
water-insoluble TiOis2 tends
because to the hydrophobic
hinder the abilityTiO 2 nanoparticles
of water vapor moleculesprevented in
the membrane,
the micro- and thereby
nano-paths in the network
prolonging the pathstructure
of water[32].
vapor Atmovement
low contents, andthe nano-TiO
reducing water
2 particles
vapor
could properly
permeation. separatehigh
However, throughout the matrix,
TiO2 contents (1.25thereby
and 1.5blocking the entry
wt.%) resulted in of water vapor.
nanoparticle The reason
aggregation,
why WVP appears
destroying to drop
the structure of significantly
the film [34].after Kadamadding nanoparticles
et al. [16]. observed could be primarily
a similar result, attributed
while El-Wakil to the
highly complex path that was generated because of the distribution
et al. [35]. demonstrated that increasing the TiO2 nanoparticle content to 1 wt.% decreased of impermeable TiO 2 nanoparticles
the WVP
throughout
of the film bythe 10%.matrix.
They Generally,
also reported thethatnanoparticles increase
the high surface the pass
energy length
caused of water
by excess TiOmolecules
2 caused the by
compelling theto
nanoparticles permeating
agglomerate molecules to randomly
(as shown by SEM)oscillate
at around
higher them [33]. As previously
nanoparticle concentrations;mentioned,this
the number ofreduced
consequently available theOH groupsconcentration
effectual reduced because of theofnanoparticles
the production and ofpromoted
hydrogenWVP bonds[16]. between
Baek
Ti–O
et al. and the hydroxyl
reported that thegroupsWVP of wasPLA; this consequently
lower reduced thewere
when the nanoparticles WVPmore of thestably
films. dispersed
Moreover,
water-insoluble
throughout the PLA TiO2films
tends[36].to hinder the ability of water vapor molecules in the membrane, thereby
prolonging the path
It was found thatofthe
water
water vapor
vapor movement and reducing
transmission water
rates of the vapor
films werepermeation.
much largerHowever,
than those highof
TiOnanofibers.
the 2 contents (1.25
Due and
to 1.5
the wt.%)
extremely resulted
small in nanoparticle
diameter of aggregation,
the nanofibers, destroying
the fine the
structurestructure
of the of the
fiber
film [34].
could Kadam etregulated.
be effectively al. [16]. observed
With PLA a similar result, while El-Wakil
as the film-forming substrate,etthe al. prepared
[35]. demonstrated
nanofiber had that
increasing
superior the TiO2 nanoparticle
hydrophobic properties.content to 1 wt.%
In contrast, the decreased
casting film the was
WVPprepared
of the film bybysimple
10%. They also
physical
reportedand
mixing thatultrasonic
the high surface energy
dispersion. TiO caused
2 wasby excess TiOin
embedded 2 caused
the the nanoparticles
interstitial spaces ofto agglomerate
PLA, which
(as shownthe
increased bycrystal
SEM) gap at higher
of PLA nanoparticle
molecules, and concentrations;
water molecules this consequently
could more easily reduced
pass the effectual
through the
composite
concentration membrane, thus reducing
of the nanoparticles andthe hydrophobicity
promoted WVP [16]. of Baek
PLA et andal. increasing
reported that the the
waterWVP vapor
was
transmission
lower when the ratenanoparticles
of the film. were more stably dispersed throughout the PLA films [36].

Figure 6. WVP of PLA/TiO nanofibers and films with different TiO contents: (a) nanofibers; (b) films.
Figure 6. WVP of PLA/TiO22nanofibers and films with different TiO22contents: (a) nanofibers; (b) films.
Columns with * mean significantly different (p ≤ 0.05).
Columns with * mean significantly different (P ≤ 0.05).
It was found that the water vapor transmission rates of the films were much larger than those of
the nanofibers. Due to the extremely small diameter of the nanofibers, the fine structure of the fiber
could be effectively regulated. With PLA as the film-forming substrate, the prepared nanofiber had
superior hydrophobic properties. In contrast, the casting film was prepared by simple physical mixing
and ultrasonic dispersion. TiO2 was embedded in the interstitial spaces of PLA, which increased the
crystal gap of PLA molecules, and water molecules could more easily pass through the composite
membrane, thus reducing the hydrophobicity of PLA and increasing the water vapor transmission rate
of the film.

3.7. Light Transmittance and Opacity

Tables 3 and 4 show the variation in the transmittance (T%) of pure PLA and PLA/TiO2 nanofibers
and films in the UV-C (240 nm), UV-B (300 nm), and UV-A (360 nm) wavelength ranges. As can
Coatings 2019, 9, 525 11 of 17

be seen, with an increase in TiO2 content, the transmittance of the nanofibers in the UV-A, UV-B,
and UV-C regions first increased and then decreased, which resulted in the agglomeration of TiO2
nanoparticles, and reached maximum values of 29.64% ± 0.91%, 28.45% ± 1.92%, and 28.16% ± 3.08%,
respectively, for PLA/TiO2 -1.0. The nanocomposite film exhibited the same trend in the UV-B and
UV-C regions; however, the highest transmittance values were 0.81% ± 0.06% and 1.90% ± 0.01%
for the PLA/TiO2 -0.75 film. The transmittance of the nanofibers was higher than that of the films
because the nanofibers were porous and less dense than the films. Further, the TiO2 content affected
the amount of UV-A light that can transmit through the film. The accretion of TiO2 to PLA fibers and
films reduced all the UV transmissions significantly (p < 0.05), thus showing strong UV light-blocking
effects because TiO2 is a kind of whitening agent and a semiconductor that has an optical band gap of
385 nm, and scatters visible light [14].

Table 3. UV light opacity of PLA-based nanofibers as a property of TiO2 content.

Fiber UVC (240 nm) UVB (300 nm) UVA (360 nm)
PURE PLA 24.91 ± 1.90 a 19.83 ± 2.00 c 19.46 ± 1.22 c
PLA/TiO2 -0.5 21.63 ± 2.28 a 19.26 ± 1.90 c 19.07 ± 1.29 c
PLA/TiO2 -0.75 23.66 ± 1.83 a 22.01 ± 2.55 a 22.09 ± 2.90 a
PLA/TiO2 -1 29.64 ± 0.91 b 28.45 ± 1.92 b 28.16 ± 3.08 b
PLA/TiO2 -1.25 17.17 ± 1.63 c 16.16 ± 1.76 d 16.12 ± 2.30 d
PLA/TiO2 -1.5 16.69 ± 0.58 c 15.91 ± 1.92 c 14.58 ± 2.57 c
a, b, c, d: Means with different letters within a column indicate significant differences (p ≤ 0.05).

Table 4. UV light opacity of PLA-based films as a function of TiO2 content.

Film UVC (240 nm) UVB (300 nm) UVA (360 nm)
PURE PLA 32.4 ± 2.15 a 46.86 ± 0.60 a 59.92 ± 0.70 a
PLA/TiO2 -0.5 0.30 ± 0.05 b 0.44 ± 0.06 c 66.31 ± 11.2 a
PLA/TiO2 -0.75 0.81 ± 0.06 b 1.90 ± 0.01 b 61.27 ± 4.10 a
PLA/TiO2 -1 0.25 ± 0.01 b 0.25 ± 0.65 c 69.88 ± 1.65 a
PLA/TiO2 -1.25 0.20 ± 0.01 b 0.19 ± 0.05 c 62.34 ± 3.05 a
PLA/TiO2 -1.5 0.18 ± 0.04 c 0.17 ± 0.03 c 60.78 ± 2.31 c
a, b, c: Means with different letters within a column indicate significant differences (p ≤ 0.05).

Xie et al. fabricated PLA/TiO2 nanoparticle biodegradable films via a solution casting method.
They reported that the UV-A transmission of the PLA film decreased from 87.67% to 0.68% when the
TiO2 content was increased from 0% to 5% [9]. The transmittance of the prepared PLA/TiO2 film was
lower than that of the pure PLA film in the visible region, which affects light absorption and scattering.
Similar results have been reported on the difference of the UV light transmittance of chitosan and
gelatin/agar films after combined with TiO2 nanoparticles [32].
Table 5 shows the opacity of the nanofibers and films as a property of TiO2 nanoparticle content.
The results showed that the metallic nature of the TiO2 nanoparticles allows both nanofibers and
films to effectively act as a barrier to the penetration of UV light while increasing their opacity. Since
TiO2 nanoparticles were present as a whitening agent in the polymer matrix, it aggrandized the
opacity, increased whiteness, and reduced the transparency of the film. However, in the case of
nanofiber, the mildly augment in opacity observed at low nano-TiO2 contents may be resulted in the
absorptive or reflective functions of the nanoparticles. Additionally, the increase in opacity at high
TiO2 contents is attributable to the partial agglomeration and self-assembly of the nano-TiO2 particles
in the matrix, which hinder light from passing through the bilayer membranes [31]. In the case of
films, PLA/TiO2 -0.75 exhibited the lowest opacity among all the films with different TiO2 contents.
The opacity of the other films was higher than that of the pure PLA film; this is possibly because of
the dispersing of nano-TiO2 in the PLA membranes, possessed larger surface of nano-TiO2 for UV
light blocking which blocked UV rays and had a better shielding effect on visible light. According
Coatings 2019, 9, 525 12 of 17

to Mallakpour et al., PVA combined with modified nano-TiO2 exhibited remarkably high absorption
and increased the opacity of the composite membranes, which was around the UV region indicating
the result. They considered that this type of nanocomposite film could be used as a coating to shield
against UV light [26]. He et al. [37] fabricated the fish skin gelatin/TiO2 nanocomposite films. They
observed that compound with nano-TiO2 could decrease the light transmittance of gelatin, however,
could effectively prevented the UV light which demonstrated our results.

Table 5. Visible light transmittance percentage (%) and opacity of PLA-based nanofibers and films as a
function of TiO2 content: (a) nanofibers; (b) films.

(a) Nanofibers (b) Films

Membrane
Visible (600 nm) (%) Opacity Visible (600 nm) (%) Opacity
PURE PLA 0.96±0.02 a 18.83 ± 2.01 a 66.5 ± 2.20 a 3.10 ± 0.35 a
PLA/TiO2 -0.5 0.48 ± 0.05 b 19.93 ± 0.94 a 0.67 ± 0.71 b 15.57 ± 0.36 a
PLA/TiO2 -0.75 0.46 ± 0.03 b 22.26 ± 0.90 b 3.05 ± 0.01 b 8.94 ± 0.059 b
PLA/TiO2 -1 0.46 ± 0.01 b 30.09 ± 2.01 c 0.54 ± 0.06 b 17.46 ± 0.38 c
PLA/TiO2 -1.25 0.44 ± 0.02 b 17.59 ± 1.00 a 0.44 ± 0.05 b 14.13 ± 0.29 a
PLA/TiO2 -1.5 0.43 ± 0.01 b 17.68 ± 0.43 a 0.32 ± 0.02 b 12.38 ± 0.20 a
a, b, c: Means with different letters within a column indicate significant differences (p ≤ 0.05).

3.8. Mechanical Properties

Figure 7 illustrates the mechanical properties (TS and EB) of PLA/TiO2 nanofibers and films with
different TiO2 contents. As can be seen, the TS of the 0.5 wt.% TiO2 nanofiber decreased by 2.31 ± 0.12
to 1.72 ± 0.11 MPa. Athanasouliaa et al. found that incorporating TiO2 into a PLA matrix decreases
the TS and EB of the nanocomposites [38]. Upon increasing the TiO2 nanoparticle content to 0.75%,
the TS of the nanofibers increased from 1.72 ± 0.11 to 2.71 ± 0.12 MPa. The TS enhanced resulting in an
augment in the internal friction in the matrix because of the addition of TiO2 nanoparticles, which
created a crystalline structure [39]. Because of its van der Waals interaction with the hydroxyl groups
of PLA molecules, the concentration of filler particles, PLA crystallinity, and the interfacial adhesion of
the fillers must be carefully considered to enhance the strength [18]. The substantial TS reduction that
was observed at high TiO2 concentrations may be attributed to the self-networking of nanoparticles
that led to their agglomeration and non-homogeneous dispersion, as this phenomenon could reduce
the longitudinal and lateral TS of the nanofibers [31]. Besides, Habiba et al. argued that the addition
of TiO2 nanoparticles into chitosan/PVA nanofibrous membranes could increase the toughness of
the nanofibrous membranes owning to the stable polymer–nanoparticle interface that enhances the
mechanical property [40].
The EB is impacted by the volume fraction and distribution of the fillers in the matrix, meanwhile,
their interaction with each other could also affect [12]. Generally, the EB of nanocomposites decreases
at a high filler content. In our study, the EB of the PLA/TiO2 nanofibers in the lateral and longitudinal
directions gradually decreased from 57.5% ± 2.5% to 17.5% ± 2.1%. This phenomenon is ascribed to
the anti-plasticization. Nano-TiO2 particles might play the part of an anti-plasticizer due to increased
interaction, lessening the free volume between the biopolymer chains and reducing film flexibility.
Similar results have been reported by Fonseca et al. and Shaili et al. [41]. Thus, as reinforcement and
agglomeration were respectively observed at lower and higher TiO2 concentrations, 0.75 wt.% was
considered the optimal TiO2 nanoparticle filler concentration for a PLA fiber matrix.
In the case of films, with an increase in TiO2 content from 0% to 0.75%, the TS of the PLA/TiO2
films significantly increased from 3.16 ± 0.15 MPa to 14.49 ± 0.47 MPa (p < 0.05). A similar result has
been reported in the latest research [42]. In contrast, the EB decreased from 62.71% to 40.61% with an
augment in TiO2 content from 0% to 0.5%. At a TiO2 content of 0.75%, the EB increased to 49.03%,
and then decreased sharply to 33.23% and 27.05%, significantly (p < 0.05). This result was consistent
with that reported by He et al., who reported that the TS of a gelatin casting film containing a certain
Coatings 2019, 9, x FOR PEER REVIEW 13 of 17

augment in TiO2 content from 0% to 0.5%. At a TiO2 content of 0.75%, the EB increased to 49.03%, and
Coatings 2019, 9, 525 13 of 17
then decreased sharply to 33.23% and 27.05%, significantly (P < 0.05). This result was consistent with
that reported by He et al., who reported that the TS of a gelatin casting film containing a certain
amount
amount of of TiO
TiO22 nanoparticles
nanoparticles increased
increased owing
owing to to strengthening
strengthening of of the
the association
association between
between protein
protein
molecule
molecule andand metal
metal oxide
oxide nanoparticles
nanoparticles [37].[37].
The
The reciprocities
reciprocities between
between PLA PLA and
and TiO
TiO22 enhanced
enhanced as as the
the quantity
quantity of of TiO
TiO22;; therefore,
therefore, it it caused
caused
the
the agglomeration
agglomeration and and inhomogeneous
inhomogeneous dispersion
dispersion of of nanoparticles.
nanoparticles. At At higher
higher TiO TiO22 contents
contents of of over
over
0.75
0.75 wt.%,
wt.%, the
the agglomeration
agglomeration of of the
the nanoparticles
nanoparticles was was intensified,
intensified, thereby
thereby destroying
destroying the the mechanical
mechanical
equilibrium system, hence
equilibrium system, hencereducing
reducingthe theTS TSand
and EBEB of of
thethe film.
film. Olevaei
Olevaei et al.
et al. foundfound
thatthat
bothboththe TStheand
TS
and
EB ofEB of a composite
a starch starch composite
containingcontaining TiO2 nanoparticles
TiO2 nanoparticles and montmorilloniteand montmorillonite at high
at high concentrations
concentrations decreased [12]. It was observed that the TS and EB values
decreased [12]. It was observed that the TS and EB values of the PLA/TiO2 membranes were higher of the PLA/TiO 2 membranes
were higherofthan
than those thosePLA
the pure of the pure
film. PLA
This film. This
indicates thatindicates that theofdispersion
the dispersion TiO2 in theoffilm TiOmatrix
2 in thehas filma
matrix has aeffect,
synergistic synergistic
whicheffect, which
enhances enhances
the the microstructure
microstructure of the film,oftherebythe film, thereby improving
improving the TS of the the
TS of the PLA/TiO film [34]. These results indicated the tiny size
PLA/TiO2 film [34]. These results indicated the tiny size of TiO2 nanoparticles made an important
2 of TiO 2 nanoparticles made an
important
impact as aimpact as a filler,
filler, filling filling the
the network network
structure of structure of the macromolecules
the macromolecules and promoting andthe
promoting
formationthe of
formation of three-dimensional
three-dimensional networks between networks between
the two the two materials.
materials.
The
The results
results indicated
indicated thatthat the
the TS
TS and
and EB EB ofof the
the nanofibers
nanofibers were were lower
lower thanthan those
thoseof ofthe
thefilms.
films.
Particularly,
Particularly, the the TSTS of
of the
the films
films were
were about
about 367%
367% higher
higher thanthan that
that ofof the
the nanofibers
nanofibers because
because the the
nanofibers were mainly subjected to local stress during tensile testing that
nanofibers were mainly subjected to local stress during tensile testing that resulted in a high load torque resulted in a high load
torque
on eachon each
fiber. fiber. However,
However, the film wasthe film was subjected
subjected to overall
to overall forces, andforces,
the tightand the tight crosslinking
crosslinking between the
between
moleculesthe molecules
rendered rendered its
its mechanical mechanical
properties moreproperties more stable.
stable. Therefore, it could Therefore,
be concluded it could
that thebe
concluded that the mechanical properties of the film
mechanical properties of the film are better than those of the nanofiber. are better than those of the nanofiber.
According
According to to these
these results,
results, 0.75
0.75 wt.%
wt.% TiOTiO22 content
content of of the
thePLA
PLAfilm filmmatrix
matrixisissufficiently
sufficiently to to acquire
acquire
well-balanced
well-balanced mechanical properties in both elastic and plastic regions, which is suitable for food
mechanical properties in both elastic and plastic regions, which is suitable for food
packaging
packaging applications
applications of of both
both nanofibers
nanofibers andand films.
films.

Figure 7. Variation in tensile strength (TS) and elongation at break (EB) of PLA nanofibers and films:
Figure 7. Variation in tensile strength (TS) and elongation at break (EB) of PLA nanofibers and films:
(a,b) nanofibers; (c,d) films. Columns with * mean significantly different (p ≤ 0.05).
(a,b) nanofibers; (c,d) films. Columns with * mean significantly different (P ≤ 0.05).
3.9. Antibacterial Property
The antibacterial properties of the nanofibers and films were evaluated for two types of model
bacteria, i.e., gram-negative (E. coli) and gram-positive (S. aureus) bacteria, under two different lighting
conditions: a fluorescent lamp source and UV-A (360 nm) irradiation. As can be seen in Figure 8,
 a TiO2 content of 0.75 wt.%, the inhibition zones of the nanofibers for E. coli and S. aureus were 4.86 ±
0.50 and 5.98 ± 0.77 mm and improved by 1115% and 1268%, respectively, as compared with those of
the pure PLA fiber. The inhibition zones of the films were 3.69 ± 0.40 and 4.63 ± 0.45 mm for E. coli
and S. aureus, respectively. It is well known that TiO2 and various TiO2-based photocatalysts can only
become active under light irradiation. Toniatto et al. reported that the bactericidal effect of
Coatings 2019, 9, 525 14 of 17
electrospinning PLA/TiO2 nanofibers against S. aureus was strong after UV irradiation, which
activated the TiO2 nanoparticles, and that the effect was influenced by the time associated to TiO2
concentration
the pure PLA film [8]. Fonseca
has almostet al.no
measured the antimicrobial
antibacterial effect of PLA/TiO
properties, whereas 2 nanocomposite
the antibacterial effect of films
the
including 8 wt.%
nanocomposite nano-TiO
film increased2 under UV irradiation
gradually and reported
with increasing amountsthe killing
of TiOeffect
2 on bacteria
nanoparticles, and
and fungi
the
achieved
highest 94.3% and
inhibition 99.9%,
ratio was respectively
achieved at [5].a TiO2 content of 0.75 wt.% for both nanofibers and films.
These
At a TiO consequences
2 content pointed
of 0.75 wt.%, thethat the antimicrobial
inhibition zones of theactivity of PLA/TiO
nanofibers 2 nanocomposites
for E. coli and S. aureus were could
be ascribed
4.86 ± 0.50 and to 5.98
the nano-TiO
± 0.77 mm 2 particles;
and improvedthis is by
consistent
1115% andwith1268%,
the findings of He as
respectively, et al. [39]. TiOwith
compared 2 has

strong
those oxidizing
of the pure PLA properties
fiber. Theunder long-wavelength
inhibition ultraviolet
zones of the films were 3.69light (320–400
± 0.40 and 4.63nm), resulting
± 0.45 mm forin
E.microbial
coli and S. death
aureus,as shown by theItexperimental
respectively. is well known results. Particularly,
that TiO 2 and active
various TiOspecies
2 -based such as hydrogen
photocatalysts
peroxide,
can hydroxyl
only become activeradicals, and irradiation.
under light superoxide anionsToniattoare generated,
et al. reportedwhich
that the might passivate
bactericidal the
effect
ofmicroorganisms
electrospinningthrough PLA/TiOthe process ofagainst
2 nanofibers cell lysis that affects
S. aureus the genome
was strong after UVandirradiation,
other intracellular
which
molecules
activated when
the TiO2the irradiated TiO
nanoparticles, 2 nanoparticles
and that the effectcontacts the microbes.
was influenced by theThus,
timehigher TiO2 to
associated contents
TiO2
result in greater
concentration generation
[8]. Fonseca et al. of ROS and
measured theaantimicrobial
substantiallyeffect
increased antibacterial
of PLA/TiO rate. Li films
2 nanocomposite et al.
demonstrated
including 8 wt.%that the bactericidal
nano-TiO 2 under UV effect of
irradiation the
and composite
reported films
the was
killing affected
effect on by
bacteria the
and lighting
fungi
conditions
achieved in their
94.3% and study
99.9%,[43].
respectively [5].

Figure8.8.Inhibition
Figure zonesofofE.E.coli
Inhibitionzones andS.S.aureus
coliand aureusasasa afunction
functionofofTiO
TiO2 2nanoparticle
nanoparticlecontent
contentininPLA
PLA
nanofibers and films under light irradiation conditions: (a,b) nanofibers; (c,d) films. Columns
nanofibers and films under light irradiation conditions: (a,b) nanofibers; (c,d) films. Columns with with *
* mean
mean significantly
significantly different (P≤≤ 0.05).
different (p 0.05).

These consequences pointed that the antimicrobial activity of PLA/TiO2 nanocomposites could be
ascribed to the nano-TiO2 particles; this is consistent with the findings of He et al. [39]. TiO2 has strong
oxidizing properties under long-wavelength ultraviolet light (320–400 nm), resulting in microbial death
as shown by the experimental results. Particularly, active species such as hydrogen peroxide, hydroxyl
radicals, and superoxide anions are generated, which might passivate the microorganisms through the
process of cell lysis that affects the genome and other intracellular molecules when the irradiated TiO2
nanoparticles contacts the microbes. Thus, higher TiO2 contents result in greater generation of ROS
and a substantially increased antibacterial rate. Li et al. demonstrated that the bactericidal effect of the
composite films was affected by the lighting conditions in their study [43].
The results of this study show that nano-TiO2 particles are efficacious in restraining both
Gram-positive and Gram-negative bacteria. However, the inhibition zones formed by the PLA/TiO2
nanocomposite fibers and films for S. aureus are larger than those for E. coli. Similar results were
Coatings 2019, 9, 525 15 of 17

reported by Salarbashi et al. [20], who observed that after the bacterial inhibition test, the vitality
of E. coli was higher than that of S. aureus, which supports our conclusion. They concluded that
this was because of the different compositions of the cell walls of Gram-negative and Gram-positive
bacteria; the cell wall of gram-positive bacteria consisted of a peptidoglycan layer with a thick wall
thickness that effectively blocked the penetration of TiO2 into the cell membrane, whereas the cell wall
of gram-negative bacteria consisted of a thin layer of peptidoglycan and an inner and outer membrane.
The structure was complex, so that it could protect bacteria from many chemical agents [10].
Due to the high specific surface area and high porosity of the nanofiber, nano-TiO2 particles were
evenly separated on the surface of the fiber membrane. Besides, the photocatalytic reaction of TiO2
was achieved by direct contact between the free radicals and test bacteria; therefore, TiO2 was fully
activated and photocatalysis occurred on its surface. TiO2 nanoparticles easily aggregated in the PLA
molecules owning to the physical stirring and mixing, which reduced the photocatalytic reaction.
Therefore, the inhibition effect of the nanofibers was more efficient than that of the films.

4. Conclusions
In this study, electrospinning and solution casting were performed to successfully prepare
PLA/TiO2 nanofibers and films, respectively. The water contact angle initially decreased and then
increased with increasing TiO2 content. Moreover, TiO2 enhanced the solubility of the film and its ability
to act as an effective barrier. Furthermore, the antibacterial activity improved under UV-A irradiation,
and nanofibers and films with 0.75 wt.% TiO2 content exhibited inhibition zones of 4.86 ± 0.50 and
3.69 ± 0.40 mm for E. coli and 4.63 ± 0.45 and 5.98 ± 0.77 mm for S. aureus, respectively. The best overall
functionality was observed for a TiO2 content of 0.75 wt.% for the PLA/TiO2 nanofibers and films.
The performance of the nanofiber was better than that of the film. Future studies are required to test
the effectiveness of the films as packaging material for real food.

Author Contributions: Data Curation, S.A.; Writing—Original Draft Preparation, S.F.; Writing—Review & Editing,
F.Z.; Project Administration, Y.L.; Funding Acquisition, Y.L.
Funding: This research was supported by Sichuan Science and Technology Program (2018RZ0034), and Natural
Science Fund of Education Department of Sichuan Province (16ZB0044 and 035Z1373).
Conflicts of Interest: The authors declare no conflict of interest.

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