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Journal of Molecular Structure 1127 (2017) 74e80

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Journal of Molecular Structure


journalhomepage:http://www.elsevier.com/locate/molstruc

Synthesis, structural characterization and antibacterial activity of cotton fabric


modified with a hydrogel containing barium hexaferrite nanoparticles

a, * b c
Desislava Staneva , Tatyana Koutzarova , Benedicte Vertruyen , Evgenia
d e, **
Vasileva-Tonkova , Ivo Grabchev
aUniversity of Chemical Technology and Metallurgy, 1756 Sofia, Bulgaria
b Institute of Electronics, Bulgarian Academy of Sciences, 1784 Sofia, Bulgaria
c LSIC, Chemistry Department B6, University of Liege, Sart Tilman, B-4000 Liege, Belgium
d Institute of Microbiology, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria
e Sofia University “St. Kliment Ohridski”, Faculty of Medicine, 1407 Sofia, Bulgaria

article info abstract

Article history: 2þ 3þ
Barium hexaferrite nanoparticles were synthesized by co-precipitation of Ba and Fe cations with NaOH under of high-
Received 30 May 2016 power ultrasound. The nanoparticles were dispersed in an aqueous solution of the hydrogel precursors. This solution was used
Received in revised form
19 July 2016 to impregnate the cotton fabric dyed with a photoinitiator. The composite material BaFe 12O19 nanoparticles-hydrogel-cotton
Accepted 20 July 2016 fabric was prepared by surface initiate photopolymerization under visible light.
Available online 21 July 2016
The modification of the cotton fabric and uniform distribution of the nanoparticles in the structure of the hydrogel were
analyzed by scanning electron microscopy (SEM), IR spectroscopy, X-ray diffraction analysis (XRD), fluorescence and
Keywords:
colourimetric analyses. The antibacterial efficacy of the material was evaluated against Gram-negative Escherichia coli and
Nanoparticles
Ultrasound Pseudomonas aeruginosa.
Hydrogel © 2016 Elsevier B.V. All rights reserved.
SEM
XRD
Antibacterial

1. Introduction magnetic properties [10,11]. Nanoparticles have been developed as contrast


agents for magnetic resonance imaging, hyperthermia agents and as carriers
In the last years, the resistance of pathogenic bacteria to almost all for targeted drug delivery to treat several types of cancer [12e14]. The
commercially available antibiotics has led to an increasing in-terest in finding magnetic nanoparticles as delivery nanosystems are considered effective new
new antimicrobial agents and identifying new strategies for the treatment of tools to tackle the cur-rent challenges in treating infections [11].
infectious diseases [1,2]. Recently, novel antimicrobial agents have been
developed using nanoscale materials [3e5]. Nanoparticles have received great Barium hexaferrite is one of the most important hard magnetic materials
attention due to their unique physical, chemical, and effective biological used for permanent magnets, magnetic recording me-dium and in the creation
properties in various fields, including medicine [6,7]. Antimicrobial and anti- of microwave components and devices such as circulators, microwaves
biofilm effect of different types of nanoparticles, especially metals or metal absorbers, etc. [15,16]. Its wide-spread use is associated with its properties -
oxides of zinc, copper, silver, gold, and iron have been reported [8,9]. high magneto-crystalline anisotropy, high Curie temperature, relatively high
Magnetic nanoparticles have been widely used in biomedical research saturation magnetization, excellent chemical stability and corro-sion
because of their biocompatibility and resistance [16].

Incorporation or immobilization of magnetic nanoparticles on textile


materials is a promising way to obtain materials with magnetic and
* Corresponding author. microwave absorption properties. The possible application of these materials
* Corresponding author. are as flexible magnetic elements in catalysis, for advanced recording, as a
E-mail addresses: grabcheva@mail.bg (D. Staneva), i.grabchev@chem.uni-sofia.
bg (I. Grabchev).
part of intelligent clothing for

http://dx.doi.org/10.1016/j.molstruc.2016.07.087 0022-
2860/© 2016 Elsevier B.V. All rights reserved.
D. Staneva et al. / Journal of Molecular Structure 1127 (2017) 74e80

Fig. 1. XRD spectra of (a) nanosized powder of BaFe12O19 and (b) modified cotton fabric.

monitoring and protecting in medicine, sport activities and in-dustry [17,18]. 2.2. Preparation of BaFe12O19 nanoparticles

BaFe12O19 nanoparticles were synthesized by co-precipitation of Ba
Cotton fabric was coated with barium hexaferrite (BaFe 12O19) doped in a 3þ
polyaniline film in order to improve the multifunctional and intelligent fabric and Fe cations with NaOH under high-power ultrasound. Ba(NO 3)2 and
with magnetic and electroconductive prop-erties. 30 wt % of nanopowders is Fe(NO3)3$9H2O were dissolved in distilled water at a ratio Ba:Fe ¼ 1:10,
necessary to obtain fabric with magnetic properties and only 5 wt % of which was suitable to obtain monophasic powder from BaFe 12O19. The ratio
nanopowders for the highest conductivity [19]. M. Grosu et al. [20] have also was not stoichiometric
found the magnetic properties of the woven fabric to depend on the mass Ba:Fe ¼ 1:10, because of the high solubility constant of the pre-cipitate of
percentage of magnetic power in the coating solution. Magnetite 3.6
Ba(OH)2 - Ks ¼ 10 at 25 C, which determined its
nanoparticles (Fe3O4) have been used to improve the antibiofilm properties of instability in an aqueous solution [23e25].
textile dressing, tested in vitro against monospecific Candida albicans biofilms The solution was homogenized with a magnetic stirrer (Boeco MMS-
[21]. However, limited information is available for using barium hexaferrite 3000) for 2 h. An ultrasonic probe (VCX750 Ultrasonic Pro-cessor at 750 W)
nanomaterials in textiles for antimicrobial purposes. was placed in the solution and concentrated NaOH was adding dropwise until
complete co-precipitation of cations. The resulting precipitate was centrifuged
and dried at 100 C. The precursor thus obtained was ground, placed in a
The aim of this study is to obtain a cotton fabric with uniformly dispersed corundum boat and subjected to high temperature treatment to obtain single-
barium hexaferrite nanoparticles on the fibre surface by means of an phase nano-sized BaFe12O19. The optimal parameters of the pro-cess were
acrylamide hydrogel and to assess their antimicrobial activity. FTIR, XRD, pH ¼ 11.5 and 120 min ultrasound treatment with pulse duration 2 s to every
SEM, EDX, fluorescence spectroscopy and col-ourimetry have been used for 4 s and amplitude - 40%. In this way the temperature for the preparation of a
the characterization of the barium hexaferrite nanoparticles and composite single-phase powder of nanosized BaFe 12O19 could be lowered by 100 C as
material. compared to a previously known technology for the synthesis of this material.
The high-temperature synthesis was performed at 800 C for 4 h in a tube
furnace Carbolite.
2. Experimental

2.1. Materials

A bleached and unmercerized, plain-woven 100% cotton fabric with a 2.3. BaFe2O19 nanoparticles-hydrogel-cotton fabric preparation
2
surface weight of 140 g m was used throughout the work. Acryl amide
(AAm),
0
N,N -methylenebisacrylamide (bis-AAm) and N- The procedure for cotton surface functionalization involved dyeing with
the modified photoinitiator eosin Y (MEY) (step 1) and subsequent hydrogel
methyldiethanolamine (MDEA), Ba(NO3)2 and Fe(NO3)3$9H2O were used formation with dispersed magnetic nano-particles by surface initiated
as obtained from Aldrich without further purification. Precosolve was
0 photopolymerization under visible light (step 2). The MEY was used as
obtained from Schill&Seilacher (Germany). 4,4 -bis(1,3,5-triazin-2-ylamino)- photo-sensitizer and methyl-diethanolamine (MDEA) as co-initiator. The
0
stilbene-2,2 -disulfonic acid were synthesized according to a method synthesis of MEY and dyeing of cotton fabric was previously reported [26].
described previously [22]. All solutions were made with distilled water. The concen-tration of the MEY was 1.0% owf.
The light sources for photopolymerization were two energy saving lamps:
The deposition of nanoparticles and hydrogel formation was performed
via the following procedure:
1. HL 8325, 25 w, 1230 Lumen, 6400 K, Horoz Electric BaFe12O19 (barium hexaferrite) nanoparticles (6 wt % to AAm and bis-
2. VO 11211, 11 w, 550 Lumen, 6400 K, Vitoone AAm) were added to an aqueous solution of surfactant
76 D. Staneva et al. / Journal of Molecular Structure 1127 (2017) 74e80

Fig. 2. SEM micrograph of BaFe12O19 nanoparticles (a) and (b) particle size distribution e diameter.

Precosolve at a concentration of 0.12 mg/ml. Next AAm (25.0% owf), bis- with modified Eosin Y.
AAm (5.0 wt % to AAm), MDEA (4.0 wt% to monomers) and triazine-stilbene
fluorescent brightener were added to the solution. The concentration of 2.6. Antibacterial efficacy assay
5
fluorescent brightener was 6.10 М. The volume of solutions was of liquor to
goods ratio 2:1. The samples of the dyed fabric were overlaid with these Antibacterial efficacy of the modified cotton material was evaluated
solutions and illuminated with two lamps emitting visible light for 5 h. against model Gram-negative bacteria Escherichia coli and Pseudomonas
aeruginosa using viable cell count method. Test cultures were grown
overnight in meat-peptone broth, and 500 mL of the obtained cell
2.4. Determination of gel fraction with nanoparticles suspensions were introduced into sterile glass tubes. Then square shape textile
specimens of 8-mm previously sterilized by UV irradiation were put into the
The samples of the composite material were measured in the dried state tubes. Uncoated cotton material was used as a control. After 24 h incubation
after photopolymerization. Then they were soaked in distilled water for 18 h up at 27 C under agitation, the samples were transferred to tubes containing 500
to a constant weight and taken out from the water in order to remove the mL of sterile saline solution and vigorously mixed for 30 min to suspend
soluble parts. The samples were dried again and measured. bacterial cells from the textile specimens. Serial dilutions were made from
each eluent and plated onto meat-peptone agar plates and incubated for 24 h
The gel fraction percentage was calculated by the following equation (1): at 27 C. The colonies were then counted, total CFU (colony forming units)
determined, and bacterial

Gel fraction (%) ¼ (W1/W2) x 100 (1)


growth reduction calculated according to Eq.:
where W2 and W1 are the weights of composite materials in the dry state
before and after soaking in distilled water, respectively. Growth reduction (%) ¼ 100 (cfu(control) e cfu(sample)/
(cfu(control)

2.5. Characterization

IR analysis was carried out on an infrared Fourier transform spectrometer 3. Results and discussion
(IRAffinity-1 “Shimadzu”) equipped with a diffuse-reflectance attachment
(MIRacle Attenuated Total Reflectance Attachment). X-ray diffraction The main problem in the ex situ application of the magnetic nanoparticles
analysis (XRD) was performed on a Bruker D8 X-ray diffractometer using a on the textile material is their precipitation in water and possible aggregation.
Cu Ka radiation source (lka ¼ 1,54057 Å) to investigate the crystalline size To avoid that and to assist the uniform distribution of the nanoparticles onto
the fibre surface, an anionic surfactant was used. Gel formation and its
and phases of the synthesized BaFe 12O19 (barium hexaferrite) nanoparticles swelling were monitored by fluorescence analysis. The nanoparticles were
and the nanoparticles immobilized onto the cotton fabric. The surface dispersed in water by an anionic surfactant and mixed with monomers acryl
morphology of the treated fabric was analyzed by scanning electron amide, bis-AAm, co-initiator of photopolymerization N-methyldiethanol-
microscope (SEM) Philips ESEM XL30 FEG. A Philips ESEM XL30 FEG 0
amine (MDEA) and fluorescence dye (4,4 -bis(1,3,5-triazin-2-ylamino)-
equipped with energy-dispersive X-ray spectroscopy (EDX) was used to
0
determinate the chemical composition of the impregnated nanoparticles. The stilbene-2,2 -disulfonic acid). The solution was applied on a cotton fabric
fluorescence spectra of the composite material were recorded using a Varian dyed with eosin Y (MEY) and irradiated with visible light as describe earlier
Cary Eclipse fluorescence spectro-photometer with resolution of 2 nm. [27].

The high surface energy of these particles makes them extremely reactive,
The colour characteristics of the fabrics were determined on a Texflach and most nanoparticles undergo aggregation without protection or passivation
ACS/DATACOLOUR with a Spectraflash 600 spectropho-tometer using D65 of their surfaces. The hydrogel was used both as a binder of BaFe 12O19
illuminant and 10 observer. The reflectance spectra (R%) were used to nanoparticles onto the cotton surface and for the prevention of their
evaluate the dyeing of the cotton fabric agglomeration. The
D. Staneva et al. / Journal of Molecular Structure 1127 (2017) 74e80

Fig. 3. SEM micrographs of modified cotton fabric (a) at magnification 37, (b) at magnification 350, (c) at magnification 3500, (d) at magnification 5000.

Fig. 4. EDX analysis of a) cotton fabric without nanoparticles (textile 10-edx1) and b) modified cotton fabric with nanoparticles (textile 10-edx2).

fraction of the resulting gel was calculated by weighing the samples after the BaFe12O19 were observed together with the peaks for the hydrogel and cotton
irradiation and after treatment with water. The obtained gel was found to be fabric. The insert presents the two spectra of synthe-sized BaFe 12O19
90.4%. (bottom) and of the modified cotton fabric (above) in the interval 2 q ¼
29e38, where the characteristic peaks of BaFe 12O19 can be observed. As
seen, the two spectra peaks coincide fully.
3.1. XRD analysis

The phase composition of the synthesized magnetic nano-particles and the


modified cotton fabric was determined by x-ray diffraction (XRD) analysis. 3.2. SEM and EDX analyses
Fig. 1a shows the XRD powder patterns of BaFe 12O19 nanoparticles. All
peaks correspond to BaFe12O19 phase and the absence of the peaks of the SEM was used to examine the grain size and morphology of the barium
other phase is evidence for the single-phase of the obtain materials. Fig. 1b hexaferrite powder (Fig. 2a). The particles are aggregated due to the strong
shows the XRD powder patterns of the cotton fabric modified with a hydrogel attractive magnetic force. The formation of clusters is typical of the magnetic
containing BaFe12O19 nanoparticles. The characteristic peaks of nanoparticles as a consequence of the attractive van der Waals and magnetic
dipole forces that act
78 D. Staneva et al. / Journal of Molecular Structure 1127 (2017) 74e80

Fig. 7. Change in the fluorescent spectra of the composite material in water with the
Fig. 5. FT-IR spectra of the cotton fabric and modified with nanocomposite hydrogel time (lext ¼ 365 nm).
cotton fabric.

cotton fabric
1.5
modified cotton fabric in dry state
K/S modified cotton fabric in wet state

1.0

0.5

0.0
400 450 500 550 600 650 700
Wavelength, nm
Fig. 8. Effect of moisture on K/S values for modified cotton fabric in the dry and in the wet
state across the visible spectra.
Fig. 6. Fluorescent spectra of the composite material in dry and wet state.

edx2). The peaks for Fe and Ba atoms appear in the presence of nanoparticles
and are evidence that the particles retain their composition after
between individual nanoparticles in a monomer liquid prior to the immobilization. The peaks for Au are due to the preparation of the sample for
polymerization [28]. The BaFe12O19 powder exhibits a narrower grain size analysis.
distribution, with the average particle size being 34 nm (Fig. 2b). The
particles have an irregular shape - something between a sphere and a
3.3. Infrared spectra of the plain cotton fabric and of the composite material
hexagonal platelet. The process of forming the platelet shape typical for the
BaFe12O19 hexagonal structure has not been completed due to the small
particle size. FTIR spectroscopy has been used to investigate the structure of the gel
Fig. 3 shows SEM micrographs of the modified cotton fabric. The fabric deposited onto the fabric. Fig. 5 shows the IR spectra of the initial cotton
structure and single fibres can be seen (Fig. 3 a). Magnetic nanoparticles have 1
fabric and of the fabric modified with a hydrogel in the 1800 cm to 1200 cm
been incorporated in the hydrogel and are distributed fairly evenly over the
1 1
surface of the cotton fibres (Fig. 3 b). At the same time, there is an region. The observed band with a maximum at 1653 cm in native cellulose
agglomeration of BaFe12O19 par-ticles caused by the action of strong is attributed to O-H bending of the adsorbed water molecules [29]. After the
hydrogel modification of the cotton fabric a new band has been observed at
magnetic forces between them (Fig. 3 c). The observed cracks of the fibre are 1 1
due to the interaction of hydrogel with electron beam of a scanning electron around 1660 cm with a shoulder at 1616 cm . The band can be assigned to
microscope (Fig. 3 d). the carbonyl amidic group of the of the acrylamide unit (CONH 2) comprised
by the hydrogel. The shoulder is due to the primary amine N-H deformation
The successful immobilization of the BaFe 12O19 nanoparticles on the vibration.
fibre surface was further confirmed by EDX. Fig. 4 shows the cotton fabric
without nanoparticles (textile 10-edx1) and the modified cotton fabric with
BaFe12O19 nanoparticles (textile 10- 3.4. Fluorescence measurements

Fig. 6 shows the emission spectra of the composite material


D. Staneva et al. / Journal of Molecular Structure 1127 (2017) 74e80

Fig. 9. Survival of P. aeruginosa and E. coli cells (CFU/mL) after 24-h treatment with modified cotton sample. Uncoated cotton material was used as a control.

magnetic nanoparticles-hydrogel-cotton fabric in the dry and wet state. In the BaFe12O19 nanoparticles exhibited good antimicrobial effect on wound-
dry state the material emits in a range from 400 nm to 500 nm with two related pathogens. After 24-h treatment, the sample reduced the growth of P.
maxima at 410 nm and 430 nm, which is a typical behavior for triazine- aeruginosa and E. coli by 68.1% and 50%, respectively (Fig. 9), which was
stilbene fluorescent brighteners in their trans-isomeric form. After the dipping rated as a good antibacterial efficacy.
into water the fluorescent emis-sion decreases significantly. Diffusion of water
through the hydro-gel continued until equilibrium swelling was attained. Fig. The main mechanism of the antibacterial effect of BaFe 12O19
7 illustrates the changes of the fluorescence spectra of the compos-ite material nanoparticles as other iron oxide or ferrite nanoparticles might be via
with the time. The insert shows that for the studied time interval the oxidative stress generated by reactive oxygen species (ROS) [7,33,34]. Some
fluorescence intensity decreases linearly as the mobility of fluorescent probes have hypothesized that reactive oxygen species (ROS) generated by
increases and they converted in their nonfluorescent cis-isomeric form [30]. nanoparticles could kill bacteria without harming non-bacterial cells [35].
The decrease of fluorescence intensity can be used to measure the diffusion ROS, including superoxide radi-cals (O2 ), hydroxyl radicals ( OH), hydrogen
coefficient of water into composite material [31,32]. The diffusion coefficient 1
peroxide (H2O2), and singlet oxygen ( O2), can cause damage to proteins and
5 2 1
was calculated as D ¼ 2,1 10 cm s . DNA in bacteria [36]. Park et al. [37] also demonstrated antibacterial ac-tivity
from silver metals due to ROS generation. In the present study, BaFe 12O19
could create ROS leading to the inhibition of the tested pathogenic cells,
The immobilization of nanoparticles onto the cotton fabric surface yielded similar to the inhibition by iron oxides described for Staphylococcus aureus
a slight brown colour of the sample. When textile was transferred from the [7,38].
dry to the wet state the colour intensified and shade shifted to red brownish.
The moisture effect on K/S values for modified cotton fabric is shown in Fig.
8. One of the reasons is the reduced light scatter, e.g. the value of S 4. Conclusion
(scattering coefficient) is reduced though hydrogel swelling. The other reason
is the fluorescence quenching of the triazine-stilbene fluorescent brightener
We have synthesized for the first time barium hexaferrite (BaFe 12O19)
from 400 to 450 nm. However K/S values increase also in the region from
nanoparticles under the conditions of an ultrasonic technology facilitating the
450 to 550 nm, but the changes in K/S values are not so significant in the
progress of the reaction at lower tem-perature and in a shorter, if compared to
region from 550 to 700 nm.
a known technology. An anionic surfactant has been used to stabilize the
nanoparticles in aqueous solution. By surface initiated photopolymerization
This difference can be attributed to the changes in the value of under visible light, a hydrogel based on acryl amide, N,N-methyl-
K (absorption coefficient). Its value is connected with the con-centration of enebisacrylamide has been used for the modification of cotton fabric and for
colour molecules (nanoparticles), which does not change when organic dyes uniform distribution and binding of the nanoparticles onto the fibres surface.
are used for dyeing. The colour of the investigated composite material is due The new composite material BaFe 12O19 nanoparticles-hydrogel-cotton fabric
to the colour of nano-particles. So, the swelling of hydrogel influences the has been prepared by surface initiate photopolymerization under visible light.
distribution and reduces agglomeration of the nanoparticles. That increases The composite material has been characterized by, XRD, SEM, FTIR,
the light absorption and influences the colour of the composite material. fluorescence and colourimetric analyses. For the first time the antibacterial ac-
tivity against Gram-negative bacteria Escherichia coli and Pseudo-monas
aeruginosa of composite textile material, containing BaFe 12O19 nanoparticles
has been investigated and the results have shown good antimicrobial effect for
3.5. In vitro antibacterial activity both wound-related pathogens.

Our results obtained for the two in vitro model Gram-negative bacteria
demonstrated that the composite material, containing
80 D. Staneva et al. / Journal of Molecular Structure 1127 (2017) 74e80

Acknowledgements [18] O. Akman, H. Kavas, A. Baykal, M.S. Toprak, A. Ҫoruh, B. Aktas¸ , Magnetic
metal
The work was supported in part by the research agreements between WBI, nanoparticles coated polyacrylonitrile textiles as microwave absorber,
Belgium, and the Bulgarian Academy of Sciences. J Magnetism Magnetic Mater. 327 (2013) 151e158.

[19] N. Onar, A. Cireli Akṣit, M. Ebeoḡlugil, I. Birlik, E. Ḉelik, I. Ṏzdemir,


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