Applied Nanoscience (2022) 12:4019–4032

https://doi.org/10.1007/s13204-022-02634-z

ORIGINAL ARTICLE

Characterization and photocatalytic activity of ­TiO2 nanoparticles

on cotton fabrics, for antibacterial masks
Marco Antonio Alvarez‑Amparán1   · Vanessa Martínez‑Cornejo1   · Luis Cedeño‑Caero1   ·
Kevin A. Hernandez‑Hernandez2,3   · Rubén D. Cadena‑Nava2   · Gabriel Alonso‑Núñez2   ·
Sergio Fuentes Moyado2 

Received: 28 June 2022 / Accepted: 30 August 2022 / Published online: 15 September 2022
© King Abdulaziz City for Science and Technology 2022

Abstract
The in-situ impregnation of two commercial cotton fabrics (lab coat and Indiolino) with ­TiO2 nanoparticles ­(TiO2-NPs) was
carried out. For this, two commercial cotton fabrics were dipped in titanium isopropoxide, titanium butoxide and titanium
tetrachloride solutions to the ­TiO2-NPs formation and in-situ ­TiO2-NPs impregnation on the cotton fabric surface by the
sonochemical, hydrothermal and solvothermal methods, respectively. The impregnated fabrics were characterized by ATR-
FTIR, SEM–EDS, Raman, UV–Vis, DRS and tension tests. The results showed the successful formation and impregnation
of ­TiO2-NPs on both cotton fabrics. The leaching of ­TiO2-NPs from cotton fabrics was negligible after several washing
cycles. The self-cleaning properties and antibacterial activity of ­TiO2-NPs functionalized cotton fabrics were assessed by
photocatalytic and antibacterial tests. The photocatalytic activity was determined by the degradation of methylene blue dye
under UV and solar irradiation. The materials showed good photoactivity, since MB was degraded up to 99% under solar
and UV irradiations in 60 min. The bactericidal capacity of the ­TiO2-NPs on fabrics, evaluated in-situ by SEM, showed that
Indiolino presented the best antibacterial properties against Escherichia coli and Bacillus pumilus.

Keywords  Titania nanoparticles · Antibacterial masks · Cotton fabrics · Sonochemical synthesis · Hydrothermal synthesis

Introduction pandemic caused by the SARS-CoV-2 virus has potentiated

the exhaustive research on this type of functionalized fabrics
The development of fabrics with antibacterial and antiviral since these ones could help avoiding the virus dispersion
activity and self-cleaning properties has been triggered in (Yocupicio-Gaxiola et al. 2021; Militky et al. 2021). The
the last decades due to healthcare industry and home tex- cotton fabrics are the main textile used in the healthcare
tiles applications (Hussain 2020; Yocupicio-Gaxiola et al. industry since the cotton surface could be electrostatically
2021; Konda et al. 2020; Botequim et al. 2012; Montazer charged, in an analogous way as on the natural silk surface
and Seifollahzadeh 2011). Moreover, the current COVID-19 (Konda et al. 2020). In this sense, since the cotton fabric is
a porous and hydrophilic material, antibacterial agents can
be added over the cotton surface. Also, the addition of an
* Marco Antonio Alvarez‑Amparán antiviral agent to the textile fibers is an interesting option as
[email protected]
additional protection to avoid virus infections for both the
* Luis Cedeño‑Caero wearer and those around them.
[email protected]
The selection of an antiviral agent should be based on
1
UNICAT, Departmento de Ingeniería Química, Facultad its antiviral activity, level of toxicity, method of applica-
de Química, Universidad Nacional Autónoma de México, tion and cost. Also, antiviral agents added to textile fibers
04510 Ciudad de Mexico, México must be active even in the presence of a wide class of
2
Centro de Nanociencias y Nanotecnología (CNyN‑UNAM), microorganisms, stable, durable, safer for the user and not
Universidad Nacional Autónoma de México, harmful to the environment. It has been shown that inor-
22800 Ensenada, Baja California, México
ganic nanoparticles (NPs) can inactivate virus due to the
3
Centro de Investigación Científica y de Educación Superior viral envelope rupture by the generation of oxidant species
de Ensenada (CICESE), Ensenada, Baja California, México

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4020 Applied Nanoscience (2022) 12:4019–4032

(Botequim et al. 2012; Ogunsona et al. 2020, Yaqoob et fabrics and were exposed to solar and UV irradiation to
al. 2020). Also, it is important to mention that inorganic corroborate the antibacterial properties of the synthetized
NPs may act as adsorbents, catalysts or photocatalysts, materials.
which could enhance or promote high antibacterial activ-
ity. Currently, inorganic NPs and their composites are
a viable alternative to manufacture multifunctional and
antiviral fibers (Hussain 2020; Yocupicio-Gaxiola et al. Materials and methods
2021). Among others inorganic NPs, ­TiO2 nanoparticles
­( TiO 2 -NPs) have attracted attention because they are Materials
biocompatible, non-toxic, and inexpensive (Yocupicio-
Gaxiola et al. 2021). The incorporation of T ­ iO2-NPs on Commercial lab coat (100% cotton, 244 g/m2) and Indi-
textile fibers provides them with antiviral properties, UV olino (100% cotton, 175 g/m2) fabrics were used as model
protection, promotes surface hydrophobicity/hydrophilic- textiles. Titanium isopropoxide ­(C12H28O4Ti, 98%), glacial
ity, could act as flame retardant, and provide self-cleaning acetic acid (­ CH3COOH, 98%), titanium chloride (­ TiCl4,
properties (Hussain 2020; Yocupicio-Gaxiola et al. 2021; 98%) and titanium butoxide (Ti(OBu) 4, 98%) were pro-
Montazer and Seifollahzadeh 2011, Lessan et al. 2011; vided by Sigma-Aldrich and used without further puri-
Senić et al. 2011). The antibacterial activity of T­ iO2-NPs fication. Before the treatments, the fabrics were washed
is attributed to the fact that they can produce reactive oxy- with a non-ionic detergent and dried for 24 h at 70 °C.
gen species (ROS) in the presence of UV irradiation, since All impregnation procedures were carried out using
­TiO2-NPs is a semiconductor material, acting as a photo- 5 cm × 5 cm of cotton squares.
catalyst. Also, ­TiO2-NPs antibacterial activity has been
observed in dark conditions, however, the action mecha-
nism is not yet fully understood (Ogunsona et al. 2020). Synthesis and incorporation of TiO2‑NPs on cotton
The synthesis of T ­ iO2-NPs by sonochemical irradia- fabrics
tion at low temperatures has been reported as an efficient
method to obtain nanocrystals of suitable size (Guo et al. Modified cotton fabrics were obtained from three synthesis
2003). In a similar sense, Prasad et al. (2010) reported the methods of T­ iO2-NPs, in each one the preparation method
synthesis of T­ iO2-NPs by the sol–gel method assisted by was improved varying the synthesis parameters, such as:
ultrasound at low temperature. Additionally, the impregna- loading of Ti precursor, treatment and synthesis temperature,
tion of several types of NPs on the surface of cotton fibers reaction time and washing conditions.
by ultrasonic irradiation has been reported previously, e.g.,
Ag nanoparticles (Hadad et al. 2007), ZnO nanoparticles
(Perelshtein et al. 2009a), CuO nanoparticles (Perelshtein Sonochemical synthesis
et  al. 2009b) and T ­ iO 2-NPs (Perelshtein et  al. 2012).
Akhavan et al. (2014) and Montazer and Seifollahzadeh The ­TiO2-NPs impregnation on cotton fibers by sonochemi-
(2011) have reported the immobilization of ­TiO2-NPs on cal synthesis was carried out according to the methodol-
cotton using the ultrasound-assisted sol–gel method, obtain- ogy proposed by Akhavan et al. (2014) and Montazer and
ing the anatase phase without requiring subsequent heating. Seifollahzadeh (2011) and it was adapted according to our
Complementary, cotton fabrics impregnated with ­TiO2-NPs purposes. Briefly, the ­TiO2 nanocrystals were synthesized
by ultrasound showed high resistance to the leaching under and simultaneously impregnated on cotton fabrics under
several washing cycles, maintaining their self-cleaning, anti- ultrasonic irradiation by hydrolysis of titanium isopropox-
bacterial, and antiviral properties (Akhavan et al. 2014). ide (IPT) in the presence of distilled water, using acetic
In this work, to obtain fabrics with antibacterial prop- acid as hydrolysis catalyst. In a typical preparation, distilled
erties, cotton fabrics with ­TiO2-NPS were synthetized by water and glacial acetic acid were placed in a flask, then the
several methods. Cotton fabrics were analyzed by ATR- solution was stirred for 5 min at room temperature (RT).
FTIR, Raman and SEM–EDS to assess the appropriate Subsequently, a 5 × 5 cm of cotton piece was immersed into
formation and impregnation of the ­TiO2-NPs on the sur- the solution and the flask was placed in an ultrasonic bath
face of the fibers. Photocatalytic degradation of methylene (Brason 2200; 50 kHz, 220 W) for 5 min at RT. Afterwards,
blue (MB) was carried out under UV and solar irradiation 1 mL of IPT was added dropwise to the solution in the bath
to assess the self-cleaning properties. The MB degrada- and the temperature was increased to 65 °C and kept con-
tion rate was discussed in terms of the pseudo-first order stant for 4 h. After the reaction time, the flask was removed
kinetic constants. Escherichia coli and Bacillus pumi- from the ultrasound bath and the cotton squares were dried
lus bacteria were incubated on the functionalized cotton

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Applied Nanoscience (2022) 12:4019–4032 4021

at RT in a desiccator for 24 h. The fabrics were washed with Photocatalytic tests
distilled water and dried at 70 °C for 24 h.
Methylene blue degradation tests using UV radiation
Hydrothermal synthesis
The photocatalytic properties of the T­ iO2-NPs functional-
The cotton samples were first dried at 70  °C for 4  h to ized cotton samples were analyzed based on the methylene
remove adsorbed water and immediately dipped for 12 h blue (MB) degradation, which was previously impregnated
into a 1 wt.% solution of titanium butoxide (BuOT) in a on the surface of the cotton fabrics. The cotton samples
mixture of tertbutanol and acetic acid (90/10 wt.%). Sam- were cut into 2.5 cm × 2.5 cm squares and were impregnated
ples were then removed and dried at 60 °C for 2 h in an with a MB solution (3 mL, 5 ppm). Then, the fabrics were
oven, to evaporate the solvent, and then transferred into a exposed to UV-light source (320 nm) with an intensity of
200 mL Teflon-lined stainless steel autoclave, half-full of 3.5 mW/cm2. The MB degradation was followed by UV–Vis
water, which was then placed in an oven maintained at the DRS of the fabric squares at 0, 15, 30, 60 and 120 min of
required temperature (i.e. 110 °C) for the hydrothermal treat- UV-light exposure. The maximum absorbance value ­(C0)
ment during 3 h. Finally, samples were dried at 50 °C for 2 h was determined by UV–Vis DRS spectroscopy. Meanwhile,
(Abid et al. 2016). the UV–Vis DRS absorption spectra of the fabrics contain-
ing MB were obtained at 0, 15, 30, 60 and 120 min of UV-
Solvothermal synthesis light exposure. The rate of dye decomposition was calcu-
lated and compared based on the C/C0 values, where ­C0 and
The procedure for the synthesis of T­ iO2 nanomaterials (Wu C represent the initial MB concentration on the impregnated
et al. 2007) was adapted to obtain NPs-TiO2 on the cotton cotton pieces and the MB concentration at the time t, respec-
samples by solvothermal method as follows, a certain vol- tively (Pakdel and Daoud 2013).
ume of T ­ iCl4 (1.0–9.0 mL) was quickly dropped into a fixed
volume of acetone (60 mL) under vigorous stirring at RT. Methylene blue degradation tests using solar
The obtained solution and cotton fabrics were transferred to radiation
a Teflon-lined autoclave and sealed. The autoclave was then
placed in an oven for solvothermal treatment at 100 °C for The photocatalytic degradation of MB using ­TiO2-NPs
12 h. After cooling at RT, the cotton fabrics were removed, functionalized cotton fabrics were also assessed using solar
washed several times with acetone and finally dried at 50 °C irradiation, in similar procedure to UV irradiation, before
for 2 h. described. In this case, the cotton samples were placed in a
The nomenclature used for the synthesized materials is container and then exposed to sunlight. The average natural
shown in Table 1, where commercial fabrics were labeled day light irradiation intensity was 4 mW/cm2, in winter from
according to the cotton fabric (I or C for Indiolino or Cot- 9 am to 3 pm in Mexico City.
ton lab coat, respectively), Ti precursor (I, B and T for IPT,
BuOT or Ti chlorine, respectively) and the method used Antibacterial tests
(U, S or H; for sonosynthesis (ultrasound), solvothermal
or hydrotreated method, respectively). The synthesis tem- Cell culture
perature, the reaction time and the Ti loading (for selected
samples, with best performance) are included as reference For the bactericidal tests of the fabrics impregnated with
in Table 1. ­TiO2-NPs, Escherichia coli (MC4100) and Bacillus pumilus
(B-41243) strains were used, which are gram-negative and
gram-positive bacteria, respectively. Escherichia coli is a

Table 1  Nomenclature of the Fabric Method Precursor Time (h) Temperature Ti (wt.%)*

synthesized materials (°C)

IIU Indiolino Sonosynthesis IPT 4 65 2.7

IBH Indiolino Hydrothermal BuOT 3 110 2.8
CIU Cotton lab coat Sonosynthesis IPT 4 65 2.6
CBH Cotton lab coat Hydrothermal BuOT 3 110 2.4
CTS Cotton lab coat Solvothermal TiCl4 12 100 n.d
*
 Evaluated by SEM–EDS

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gram-negative bacterium, rod shaped (2.0–6.0 µm in length) to corroborate the formation and successfully impregnation
bacteria with rounded ends (Conti and Gettner 1962; Per- of ­TiO2-NPs on the cotton fabrics. Raman spectroscopy and
cival et al. 2014). Bacillus pumilus is a gram-positive bac- DxR Raman microscope Thermo Scientific was used to cor-
terium, rod shaped (0.5–10 μm length) bacteria (Borsa et al. roborate the surface characteristics of the materials. The syn-
2016; Grutsch et al. 2018). A freshly bacterial culture was thesis solutions and the water from the washing tests were
prepared for each of the bacteria to study the bacterial activ- analyzed by UV–Vis spectroscopy at RT (Varian Cary 50)
ity of the samples. From an overnight culture of E. coli and from 200 to 1100 nm to assess the impregnated Ti amount
B. pumilus, 900 μL were taken and added to 45 mL of fresh and the leached Ti amount, respectively. Scanning electron
LB medium. Then the bacterial mediums were incubated microscopy (SEM) coupled to energy dispersive spectros-
using a New Brunswick Scientific G-25 Incubator Shaker, copy (EDS) system was carried out using a Jeol JSM-5900
at 150 rpm and 37 °C, until their optical density reached 0.1 LV microscope to the morphological and elemental analysis.
at 600 nm ­(OD600 = 0.1). The optical density of the bacte- Surface area of cotton samples was determined using N ­ 2
rial culture was measured using a Thermo Multiskan GO adsorption–desorption isotherms at – 196 °C on a Tristar
spectrophotometer at 600 nm. Micrometrics apparatus; the samples were degassed 8 h in
vacuum at 350 °C. Tensile strength of the samples chemi-
Bactericidal activity of TiO2‑NPs on fabrics cally treated and without treatment were tested on a Digital
traction force Gauge, LZKW. The MB degradation on the
To study the bacterial activity, 4 μL of fresh bacteria culture surface of the cotton pieces was analyzed by UV–Vis diffuse
was placed on squares fabrics of 0.5 × 0.5 cm. Then, the reflectance spectroscopy (UV–Vis DRS) by a Perkin Elmer
fabric pieces inoculated with bacteria were exposed to UV Lambda 365.
radiation (254 nm) using an Air Science UV-Box decontami-
nation chamber. The fabrics were irradiated with UV light
(254 nm) for 2.5 and 5 min on both sides. Subsequently, the Results and discussion
cloth samples were incubated in petri dishes with LB agar
for 18 h at 37 °C to study antibacterial activity. SEM–EDS micrographs and elemental mapping

Bactericidal in‑situ study by SEM All fabrics were analyzed by SEM–EDS. It is important to
note that to obtain nano size particles, an optimum Ti load-
After the samples were incubated, the antibacterial activity ing should be immobilized on the cotton fabrics so as not
was analyzed by SEM Hitachi SU3500. The samples were to lose Ti species in the washing process by leaching. The
dried at RT and placed on a sample holder using carbon cotton fabrics shown in Table 1 have an optimum Ti loading
tape. Then, the samples were analyzed at low vacuum condi- and, therefore only the highest Ti loading samples showed
tions (25 Pa) and 7 kV. The images were taken at different SEM–EDS signal due to the sensibility of the technique.
magnifications (47X, 270X, 370X, 2000X and 3000X) and Since those nano particles would only be observed appropri-
recorded digitally. ately by the TEM. Therefore, the SEM technique helped to
select the optimum Ti loading corresponding to NPs domain
Washing tests (reported in Table 1).
Figure 1 shows the micrographs and elemental mapping
The cotton pieces were subjected to several washing cycles of selected impregnated cotton fabrics. Figure 1a corre-
to determine the leaching of the ­TiO2-NPs. The washing sponds to the impregnated lab coat fabrics by sonochemical
cycles were carried out according to the textile standard method (CIU) at 100X resolution. From Fig. 1a can be sug-
FZ/T 73,023–2006 as follow: the cotton fabrics impreg- gested the correct synthesis method since the observed size
nated with T
­ iO2-NPs were immersed in an ultrasound device of ­TiO2 corresponds to the NPs domain. Figure 1b shows
(100 Hz) at 40 °C for 5 min. The washed cotton fabrics were the micrograph at 1000X resolution and it can be observed
removed and rinsed with distilled water. Afterwards, the cot- that the cotton threads are covered by ­TiO2-NPs (white dots)
ton pieces and the washing water were analyzed by UV–Vis with an adequate particle size distribution on the cotton sur-
DRS and UV–Vis spectroscopy (respectively) to determine face as it was also observed in Fig. 1a. Figure 1c shows the
the amount of ­TiO2-NPs leached (Akhavan et al. 2014). micrograph of cotton fabric without supported ­TiO2-NPs.
Figure 1d shows the elemental mapping of Ti, confirming
Characterization the adequate Ti distribution on the cotton fabric. For com-
parison purposes, Fig. 1e and 1f show a sample with high
Attenuated total reflectance infrared spectroscopy (ATR- Ti loading than the cotton fabric shown in Fig. 1a and 1b.
FTIR) was carried out in Nicolet 6700 FTIR spectrometer Both micrographs shown the microparticles domain of these

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Applied Nanoscience (2022) 12:4019–4032 4023

Fig. 1  Micrographs and elemental mapping of CIU (a–d) and fabrics with high Ti loading (e and f)

samples with high Ti loading. Similar results (no shown) tensile strength of the cotton fabrics. The tensile strength of
were obtained for all fabrics. the fabrics was assessed using the bare cotton fabrics and
after a first and a second treatments. The surface area of
Tensile and textural properties of fabrics the cotton fabrics is too low, less than 1 ­m2g−1, which is a
typical value for cotton fabrics. Also, due to this low value
The Table 2 shows the surface area determined by ­N2 phys- of surface area, the immobilization of the T ­ iO2-NPs should
isorption, the lattice thread diameter, the grammage and the be carried out in a proper way to avoid T ­ iO2-NPs leaching

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Table 2  Tensile properties of the cotton fabrics

Surface area Lattice thread Grammage Tensile strength of bare Tensile strength after 1st Tensile strength
­(m2/g) diameter (mm) (g/m2) cotton fabrics (N) treatment (N)a after 2nd treatment
(N)b

Indiolino 0.4 0.38 175 9.90 15.22 13.82

Lab coat 0.6 0.30 244 8.33 10.39 9.21
a
 1st treatment: ultrasound for 2 h and dried for 24 h at 65 °C
b
 2nd treatment: ultrasound for 5 h and dried for 24 h at 110 °C

due to the saturation of OH- surface groups on the cotton by acid hydrolysis (Akhavan et al. 2014). In addition, shrink-
fabrics. According to the previous SEM–EDS results, the age might occur while sonication causing a slight increase
morphological characteristics suggested that T ­ iO2-NPs was in breaking elongation from 5 to 6%. The results indicated
successfully synthetized and as will be seen later, the immo- that in-situ sonosynthesis of T ­ iO2-NPs on the cotton fabric
bilization of ­TiO2-NPs was carried out satisfactorily. did not cause any significant damage to on the structure of
The lattice thread diameter of lab coat and Indiolino is cotton, as has also been stated by Akhavan et al. (2014).
very similar, the difference is only 0.08 mm, which indi- In contrast, the fabric prepared by solvothermal method
cates the great similarity of both cotton-derived fabrics. (CTS) from T ­ iCl4 at 100 °C in the autoclave produces HCl.
Also, this feature explains in great manner the low value of Therefore, strong acidic condition of reaction solution pro-
surface area since the cotton fabrics are made up of inter- vokes the destruction of the structure of cotton. Even neu-
twined threads. Additionally, the thin structure of the cot- tralizing the acid conditions, was not possible to preserve
ton fabrics threads emphasizes that their surface can only the structure of cotton and this preparation method was
be coated by very small structures such as nanoclusters or discarded.
nanoparticles. The grammage represents the cotton fabric
weight per unit area and as it can be observed, its value is Raman spectroscopy
greater for the lab coat cotton than for Indiolino. The gram-
mage value difference is due to the density values that are Cotton fibers are composed of the biopolymer β-cellulose
slightly different due to the final preparation of the fabrics. (Fig.  2), whose repeating units are β-D-glucose mol-
Therefore, it could be inferred that lab coat cotton fabrics ecules and are linked by β-1,4-glucoside bonds (Pakdel
present a greater interaction with ­TiO2-NPs on their surface. and Daoud et al. 2013). Its fibers have a great amount of
The tensile strength of the cotton fabrics, without and with hydroxyl groups on the cellulose surface, so that extensive
ultrasound treatments, is an important characteristic since research have been made about the chemical functionaliza-
the immobilization of T ­ iO2-NPs could largely depend on tion of this material taking advantage of this high reactive
this property. That is, in addition to the fact that T
­ iO2-NPs functional group (OH-). The reactivity of cotton is a func-
immobilization on the cotton fabrics surface is a function of tion of the considerable number of hydroxyl groups located
physisorption and to the chemisorption phenomena, prob- on the C2, C3 and C6 carbons in each β-D-glupiranose or
ably ­TiO2-NPs interaction with OH- surface groups could anhydroglucose unit (Pakdel and Daoud 2013; Al-Taweel
also be influenced by the mechanical stability of the inter- and Saud 2016).
twined threads of cotton fabrics. Breaking loads of Indiolino Al-Taweel and Saud  (2016) stated that the ­TiO2-NPs
and Lab coat fabrics were 9.90 and 8.33 N, respectively. can interact strongly with surface hydroxyl and carboxyl
After first treatment (the immersion of cotton fabrics in an groups of cotton cellulose. Additionally, Pakdel and Daoud
ultrasound bath for 2 h and then a drying process at 65 °C),
the fabrics were about 54 and 25% more resistant than
the pristine one. The acidic condition of reaction solution
(pH = 3.5) and ultrasonic irradiation did not cause destruc-
tion on the structure of cotton. After the second treatment
(the cotton fabrics were maintained for 5 h under ultrasound
irradiation and finally a dried process at 110 °C), the fabrics
were about 10% less resistant than fabrics with only one
first treatment but were more resistant than untreated fabrics.
This loss on tensile strength fabric could be related to the
ultrasonic irradiation and/or cleavage of the cellulosic chains Fig. 2  β-D-glucose molecules

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Applied Nanoscience (2022) 12:4019–4032 4025

(2013), Daoud and Xin (2004) and Daoud et al. (2005) pro- published literature (Al-Taweel and Saud 2016). These
pose an anchoring mechanism for T ­ iO2/SiO2 composites on bands are assigned to the extension of the Ti–O bond (Eg)
the cotton surface where nanoparticles are anchored on the at 639 ­cm−1, the bending of the Ti–O bond (A1g + B1g)
hydroxyl groups of the C2, C3 and C6 carbons in cellulose. at 517 ­cm−1 and the bending of the O-Ti–O bond (Eg) at
Therefore, it can be suggested that T
­ iO2-NPs synthetized and 397 ­cm−1. It can be observed a red shift in the Eg mode
immobilized by ultrasonic irradiation as in this work, could frequencies for the T ­ iO2-NPs supported on the cotton fab-
be anchored on the surface of cotton fabrics in a similar way rics, i.e., the band at 151 ­cm−1 for the supported ­TiO2-NPs
as commented above. In this sense, the Fig. 3 shows the (see Fig. 3c) correspond to the red shift of the band at
Raman spectra of Degussa P25, IIU and CIU. From Fig. 3a it 145 ­cm−1 for ­TiO2-anatase nanoparticles.
can be observed the strong absorption at 151 ­cm−1 (Eg) cor- According to Abid et al. (2017), the red shift could be
responding to the vibrational mode of anatase T ­ iO2 NPs and attributed to the phonon confinement effect due to the
less intense bands at 398 ­cm−1 (B1g o A1g and B1g), also minor size of the T ­ iO2-NPs and the crystallinity increase.
for this phase. The bands at 514 ­cm−1 (Eg) and 643 ­cm−1 Even, the interaction between ­TiO2-NPs and -OH groups
(A1g) are assigned to rutile phase of TiO2, according to on the cotton fabric could contributed to this effect. For
Qina et al. (2009), Burlacov et al. (2006) and Hana et al. Indiolino prepared by ultrasound irradiation (IIU) (Fig. 3b)
(2018). The observed red shift for the bands is because the it can be observed an intense band at 152 ­cm−1 and less
increase of critalinity of the sample and, also could be by the intense bands at 650 ­cm−1, 1741  ­cm−1, 2913  ­cm−1. The
interaction of anatase and rutile ­TiO2 phases. first two bands could be related to anatase ­TiO2-NPs and
The observed bands at 1094, 578, 516, 433 and the bands at 1741 ­cm−1, 2913 ­cm−1 could be assigned to
383 ­cm−1 for CIU (Fig. 3c) corresponding at vibrational the characteristic vibrational modes of cellulose and T ­ iO2
modes of cellulose. According with Abid et al. (2017), phases. As for CIU, the red shift in the IIU Raman spec-
the most intense band at 1094 ­c m −1 could be assigned trum can be explained by the minor size of the T ­ iO2-NPs
to the C–O–C symmetric and assymetric stretching mode and/or the interaction between surface -OH groups of cot-
of the glycosidic bonds of the celulose`s glucopyranose ton fabrics and ­TiO2-NPs. From these results, for both IIU
ring. Figure 3c shows the vibrational modes at 144, 151, and CIU, the presence of T ­ iO2-NPs intense bands allows
383, 516, 513 and 638 ­c m −1, which are characteristics to suggest the adequate functionalization of the cotton
to ­TiO2-anatase nanoparticles, in agree accordance with fabrics.

Fig. 3  Raman spectra of a
Ti Degussa P25, b Indiolino
prepared by ultrasound irradia-
tion (IIU) and c cotton lab coat
prepared by ultrasound irradia-
tion (CIU)

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alone does not show the increasing absorption band below

800 ­cm−1, which allowed to corroborate that this region can
be attributed to the presence of ­TiO2-NPs.

UV–Vis spectra of reaction and washing solutions

Figure 5 shows the UV–Vis spectra of the preparation and

washing solutions of the synthetized fabrics. T ­ iO2 spectrum
presents an absortion band at ~ 270—280 nm and therefore
it is possible the identification of the T
­ iO2-NPs in the prep-
aration and washing effluents (Akhavan et al. 2014). It is
important to note that ­TiO2-NPs physically adsorbed on the
fabric surface are likely to leach into the washing solution.
The spectrum of CIU prepared with an excess of IPT and the
CIU prepared with an adequately amount of IPT are shown
in Fig. 5 (a and b, respectively). The CIU prepared with
an excess of IPT showed the greatest absorbance of the all
Fig. 4  FTIR-ATR spectra of: a cotton fabric, b CIU without washing, analized samples. The UV–Vis spectrum of CIU prepared
and c CIU after 5 washing cycles with an adequately amount of IPT shown an absortion band
around of ~ 270—280 nm, which is less intense than the
sample with an excess of IPT. CBH, IBH and IIU samples
Attenuated total reflectance infrared spectroscopy showed even lower values of absortion. Also, the UV–Vis
(FTIR‑ATR) analysis of subsequent washing solutions showed no absorp-
tion bands suggesting that the ­TiO2-NPs do not leach from
Figure 4 shows the FTIR-ATR spectra of the cotton lab coat the fabric surface. The above results indicated that the good
fabric and CIU. The bands at 1161 and 1030 ­cm−1 corre- immobilization of ­TiO2-NPs on the cotton fibers.
spond to the tension vibration of the functional groups C–C It is important to mention that ­TiO 2-NPs could be
and C-O of cellulose, respectively. For all samples, a broad anchored on hydroxyl and/or carboxyl groups by covalent
band between 3336 and 3280 ­cm−1 is observed, which is linkages (Akhavan et al. 2014). The chemically anchored
characteristic of O–H functional groups in cellulose (Ugur ­TiO2-NPs on the hydroxyl and carboxyl groups of the cotton
et al. 2010). surface must be the preponderant species that persist after
These bands, characteristic of cellulose and observed in
cotton fabric, persistent in CIU without and with washing
treatment showing that the textile was not modified appre-
ciably. Only was observed to shift of these bands to high
wavelengths values, it could be attributed to the interaction
of ­TiO2-NPs to cotton surface.
From 800  ­cm−1 toward longer wavelength, it can be
observed the evolution of a broad region. According to
Praveen et al. (2014) the region from 1000 ­cm−1 to 400 ­cm−1
correspond to the Ti–O stretching and Ti–O-Ti bridging
stretching modes of the T ­ iO2-NPs. Also, it is reported that
around 450 ­cm−1 presents absorption band which is attrib-
uted to the ­TiO2 NPs. The lack of definition in Fig. 4 below
800 ­cm−1 is due to FTIR-ATR was carried out with a dia-
mond crystal with a range 4000–550 ­cm−1, which does not
allow a good definition of this region. However, the obtained
results allow to establish the presence of ­TiO2-NPs (crystal-
line ­TiO2-anatase phase) on the cotton fabric surface. Fig-
ure 4 shows the FTIR-ATR spectra of the CIU before and
after washing processes (Fig. 4b-c). As reference, the spec-
Fig. 5  UV–Vis spectra of washing effluents: a CIU prepared with
trum of the alone cotton fabric is shown (Fig. 4a). It can be excess of IPT, b CIU, c CBH, d IBH, e IIU andf water solution as
observed that the FTIR-ATR spectrum of the cotton fabric reference

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Applied Nanoscience (2022) 12:4019–4032 4027

the washing tests, in agreement with Akhavan et al. (2014) by the shock waves and the growth rate of the nanocrystals
and Montazer and Seifollahzadeh (2011). is a function of the microturbulence.
According to Ugur et al. (2010), the simultaneous synthe-
sis of T
­ iO2-NPs and the functionalization of cotton fibers in Photocatalytic activity
a one-step process by sonochemical irradiation can be rep-
resented by a hydrolysis reaction (Eq. 1) and a condensation The photocatalytic activity of the ­TiO2-NPs on cotton fabrics
reaction (Eq. 2) as follow: was assessed to corroborate the self-cleaning properties and
the antiviral and antibacterial features. Since as it has been
(1)
( )
Ti OC3 H7 4 + H2 O → (Ti − OH)n + C3 H7 OH established the ROS generation is a key factor. In this sense,
the photocatalytic degradation of model molecules such as
(Ti − OH)n → (Ti − O − Ti)m + H2 O (2) dyes has been carried out as elsewhere (Hosseini‑Sarvari
et  al. 2022; Skiba and Vorobyova  2020). In this sense,
The formation of T ­ iO2-NPs can be explained in two steps 5 × 5 cm squares of the fabrics were impregnated with MB
as follow: 1) The hydrolytic Ti species, formed by the IPT (methylene blue) solution (10 ppm) and subsequently irradi-
hydrolysis in water, are condensed in many gel nuclei units ated with UV (320 nm) or solar irradiation. The adsorbed
and then are aggregated in large clusters. 2) The ·OH and ·H amount of MB did not exceed 5% for all cotton samples,
radicals, formed by the water sonolysis due to the cavitation which is indicative of the low adsorption capacity of the
process by the ultrasound irradiation, promote the hydrolysis material, due mainly to the low surface area of the materi-
of IPT and the polycondensation of Ti–OH groups, generat- als (see Table 2). Due to the characteristic blue color of the
ing the T
­ iO2-NPs. According to Ugur et al. (2010), the sono- Indiolino cotton fabric it was not possible to determine the
chemical formation of ­TiO2-NPs is carried out in the liquid MB degradation by DRS. For this reason, white color cotton
phase, around the collapsing bubble and not within the col- indiolino was used for the photodegradation tests. Prior to
lapsing cavity. The ­TiO2-NPs generation is a function of the irradiation, the 5 × 5 cm squares were cut off in four parts
microturbulence and the shock waves. The microturbulence (2.5 × 2.5 cm) and were placed in a set-up in such a way that
is due to the radial liquid movement by the cavitation of the all samples were irradiated with the same intensity. Further,
bubbles. The shock waves are a result of the high-pressure the set-up was stored in the darkness for 1 h to discard any
waves emitted by collapsing bubbles. The conjunction of possible change in the concentration, resulting from the pho-
microturbulence and the shock waves phenomena generates tolysis process (Abid et al. 2016). Figure 6 shows the MB
a localized heat and pressure transient zones. Large tempera- degradation on IBH under solar (Fig. 6b to 6e) and under
ture and pressure gradients cause water sonolysis, therefore UV irradiation (Fig. 6g to 6j). It can be observed a notice-
·OH and ·H radicals are generated and promoting the Ti–OH able decrease of the blue color on the cotton fabrics after UV
condensation. It is proposed that nucleation ratio increases and solar irradiation. The discoloration observed was due

Fig. 6  MB degradation on IBH samples under solar irradiation (b to e; at 15, 30, 60 and 120 min, respectively) and under UV irradiation (g to j;
at 15, 30, 60 and 120 min, respectively). a bare IBH and f IBH impregnated with MB solution

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to the photocatalytic degradation of MB by the T ­ iO2-NPs Meanwhile, the pseudo-first order kinetic constants under
presence, showing the efficiency of the functionalized cot- solar irradiation are higher for Lab coat than Indiolino fab-
ton fabrics. rics. The kinetic constants are: 0.0165 for CIU vs. 0.0142 for
Also, the changes of the MB concentration on the fabrics IIU and 0.0154 for CBH vs. 0.0117 for IBH.
were determined by UV–Vis DRS absorption at 0, 15, 30, The higher pseudo-first order kinetic constants values for
60 and 120 min of light exposure. According to Uddin et al. Indiolino fabrics compared with cotton fabrics, under UV
(2007), the observed band at 664 nm is assigned at dimeric irradiation, probably could be because the lightly longer size
and trimeric MB species adsorbed on the surface. The MB of ­TiO2 crystals for Indiolino fabrics, since as it has been
degradation was determined as the total MB conversion, by stated the ­TiO2 particles of larger size are more photoactive
the C/C0 relationship. Figure 7 shows the MB degradation, under shorter wavelengths, UV spectrum (Senić et al. 2011;
using IBH under UV irradiation in the photoreactor. It can Uddin et al. 2007). Contrarily, the higher photoactivity for
be observed that MB was degraded almost 70% in 60 min. cotton fabrics, under solar irradiation, it can be explained
It is important to mention that the MB degradation of CIU by two effects or by the combination of both. The first one
(not shown) was near to 99% in 60 min under UV irradia- could be due to the shorter size of T ­ iO2 crystals for cotton
tion. Also, it was observed negligible change in the MB con- fabrics which could absorb longer wavelength photons, in
centration in the presence of bare cotton fabric under UV visible spectrum. The second one could be due to the greater
or solar irradiation, which confirmed the effective role of amount of the irradiated photons under solar irradiation.
the ­TiO2-NPs in the photocatalytic activity. Based on these Figure 8 shows the MB degradation using CIU under sun-
results it is possible to infer that IPT is a better option as Ti light irradiation. It can be observed that almost a complete
precursor than BuOT. MB degradation was achieved in 120 min. Additionally, the
The MB degradation data were well fitted with a pseudo- Table 3 show that the pseudo-first order kinetic constant
first order kinetics. Table 3 shows the kinetic results of MB for CIU under solar irradiation was higher than pseudo-first
degradation using the lab coat and Indiolino fabrics pre- order kinetic constants for IBH and IIU (1.4 and 1.2 times,
pared by sonochemical or hydrothermal methods. Under UV respectively). The aforementioned results confirmed the
irradiation, for the fabrics synthesized by different method higher photoactivity of functionalized cotton lab coat fab-
and Ti precursor, it can be observed that pseudo-first order rics compared to the functionalized Indiolino fabrics under
kinetic constants for Indiolino fabrics (IBH and IIU) are solar irradiation.
higher than for the cotton fabrics (CBH and CIU); 0.01
vs. 0.0067/min and 0.0117 vs. 0.0075 ­cm−1 (respectively).

Fig. 7  DRS results of MB degradation on IBH, obtained by UV irra- Fig. 8  DRS results of MB degradation on CIU, obtained by sunlight
diation irradiation

Table 3  Kinetic results of MB photo degradation of NPs-TiO2 on cotton fabrics by solar light (sun) or UV irradiation (uv)
CIU sun CIU uv CBH sun CBH uv IBH sun IBH uv IIU sun IIU uv

K ­(min−1) 0.0165 0.0075 0.0154 0.0067 0.0117 0.0100 0.0142 0.0117

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Applied Nanoscience (2022) 12:4019–4032 4029

Fig. 10  Antibacterial activity of the fabrics on petri dish LB-agar.

Sample 1: IIU, sample 2: IBH, sample 3: CIU, sample 4: CBH. Con-
trols samples (5 and 6) correspond to cotton lab coat and Indiolino,
Fig. 9  Characteristic degradation time (τ) of MB for all synthetized respectively
cotton fabrics under UV or solar (sun) irradiation

The characteristic degradation time (τ) is the time needed 4), showed the shorter bacterial inhibition capacity. It is
to degrade half of the contaminant species present in the important to note that Indiolino without T ­ iO2-NPs (sample
experiment. Figure 9 shows the τ of MB under UV or solar 6) showed bactericidal capacity, in a minor amount of its
irradiations. For all samples (CIU, CBH, IBH and IBU), τ counterparts that contain ­TiO2-NPs. The halo of bacteria
was reached faster under solar irradiation than under UV around the Indiolino fabric in sample 6 is more homogene-
irradiation. That is, the same cotton fabric (cotton lab coat ous than the other ­TiO2-NPs treated fabrics.
or Indiolino) prepared by the same method and Ti precur- Based on the bactericidal results obtained in the Petri
sor and used under solar irradiation showed a greater MB dishes, the in-situ antimicrobial activity analysis was car-
degradation than when UV radiation was used on the same ried out by SEM only for IIU sample and its corresponding
fabrics. These results are according to the reported pseudo- control. The E. coli and B. pumilus bacteria was grown on
first order kinetic constants in Table 3 discussed earlier. the surface of the Indiolino fabric (control sample), which
This behavior could be due to the simultaneous effect of the can be observed in the SEM micrographs in Fig. 11a and
shorter size of T
­ iO2 crystals for cotton fabrics (which absorb Fig. 11c. In both cases it was possible to observe the bac-
visible irradiation) and the greater amount of the irradiated teria at 2000X magnification (see Fig. 11b y 11d and it can
photons under solar irradiation. In general, the functional- be observed that the bacteria cover most of the Indiolino
ized cotton samples synthetized in this work shown an ade- surface. The E. coli (Fig. 11b) and B. pumilus (Fig. 11d)
quately structure and a successful photocatalytic behavior as bacteria show no apparent damage, and it is observed a
has been discussed previously. normal morphology and size, in agree with (Percival et al.
2014; Grutsch et al. 2018). In the case of T­ iO2-NPs treated
Bactericidal activity of ­TiO2‑NPs on fabrics Indiolino fabric, the bactericidal activity was significantly
appreciated by means of SEM, see Fig.  12. Fig  12a, b
The bactericidal activity of the fabrics synthesized was not show the fabrics at low magnification (1300X) where the
possible to study by Kirby-Bauer technique because these homogeneous deposition of the T ­ iO2 and bacteria can be
ones do not form inhibition region, which has also been pre- observed. In Figure b and Figure d, the bacteria E. coli
viously reported with fabrics impregnated with ­TiO2-NPs and B. pumilus can be seen in greater detail (see insets).
(Singhal et al. 2021). For this reason, fabrics squares of In both cases, the areas without T ­ iO 2-NPs showed the
0.5 cm × 0.5 cm from IIU, IBH, CIU and CBH were inocu- presence of bacteria, that is the bacteria grew in zones
lated with the E. coli bacteria and were evaluated in Petri without ­TiO2 deposits, which demonstrates the ability to
dishes with LB-agar medium. After the inoculation without inhibit both bacteria. When the samples are irradiated with
UV irradiation, it was found that the IIU sample, ­TiO2-NPs UV irradiation for 2.5 min on both sides, it is possible to
impregnated Indiolino fabric by sonosynthesis and using iso- observe a greater bactericidal capacity on the fabric sur-
propoxide as Ti precursor, has a greater capacity to inhibit face, see Fig. 13. The Fig. 13a shows the E. coli biofilm
E. coli, (see Fig. 10, sample 1). Also, CIU showed good with abnormal morphology or damage. From Fig. 13b it
antibacterial capacity (sample 3). The fabrics prepared by can be observed that bacteria only grew on areas without
hydrothermal method, IBH (sample 2) and CBH (sample NPs, as was analyzed for the other Indiolino fabrics. In the

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Fig. 11  SEM micrographs of
Indiolino fabric inoculated with
E. coli (a) and B. pumilus (c).
Micrographs at 2000X magni-
fication for E. coli (b) and B.
pumilus (d)

Fig. 12  SEM micrographs at
1300X of T ­ iO2-NPs treated
Indiolino fabric and inoculated
with E. coli (a) and B. pumilus
(c). Micrographs at high mag-
nification (> 1300X) for E. coli
(b) and B. pumilus (d)

case of the fabric inoculated with B. pumilus, the bacteria sides, both bacteria were no longer found in the fabric with
were totally eliminated (see Fig. 13c) under UV irradia- and without ­TiO2-NPs.
tion. Additionally, bacteria were not found on the fabric The IIU sample showed the best bactericidal capacity,
surface, even the areas without NPs are free of bacillus. which could be due to a better distribution of the NPs on
When the Indolino fabrics were exposed for 5 min on both Indiolino surface when the sonosynthesis method is used.

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Applied Nanoscience (2022) 12:4019–4032 4031

Fig. 13  SEM micrographs of treated ­TiO2-NPs Indiolino fabric under UV irradiation for 2.5 min on both sides (5 min total), inoculated with E.
coli (a) and B. pumilus (c). Micrograph magnifications of E. coli (b) and B. pumilus (d) on the Indiolino fabric

According to the in-situ SEM analysis, the better the nano- Supervision: SFM; Validation: MAAA; Visualization: MAAA; Roles/
particles are distributed, the greater the antimicrobial effect Writing—original draft: MAAA; Writing—review & editing: MAAA.
that results. Therefore, the homogeneity of the T­ iO2-NPs on
Funding  This work was funded by the Dirección General de Asun-
the surface fabric should be considered to have an efficient tos del Personal Académico (DGAPA) of the Universidad Nacional
bactericidal capacity. Autónoma de México (UNAM) by the Research Support Program
(PAPIIT, project IV100121).

Conclusions Declarations 

Titania nanoparticles ­(TiO2-NPs) were successfully syn- Conflict of interest  On behalf of all authors, the corresponding author
states that there is no confict of interest.
thesized and simultaneously immobilized on cotton fab-
rics by several methods. The synthesis of T ­ iO2 anatase and
its impregnation was confirmed by UV–Vis, SEM–EDX,
Raman and FTIR-ATR spectroscopy. References
The leaching of the ­TiO2-NPs from the cotton fabrics
Abid M, Bouattour S, Conceição DS, Ferraria AM, Ferreira LFV,
after washing cycles was analyzed by UV–Vis and the char-
Botelho do Rego A. M, Vilarc MR, Boufi S, (2016) Hybrid cot-
acteristic band of anatase ­TiO2-NPs was observed at a very ton–anatase prepared under mild conditions with high photocata-
low intensity suggesting the adequate impregnation of the lytic activity under sunlight. RSC Adv 6:58957–58969. https://​
­TiO2-NPs on the cotton fibers. doi.​org/​10.​1039/​C6RA1​0806G
Abid M, Ferraria BS, AM, Conceição DS, Carapeto AP, Ferreira LFV,
The ­TiO2-NPs functionalized cotton fabrics degraded
Botelho do Rego AM, Chehimi MM, Vilar MR, Boufi S, (2017)
99% of methylene blue in 60 min by photocatalysis under Facile functionalization of cotton with nanostructured silver/tita-
UV and solar irradiation confirming self-cleaning properties. nia for visible-light plasmonic photocatalysis. J Colloid Interface
The bactericidal capacity of the impregnated T ­ iO2-NPs, Sci 507:83–94. https://​doi.​org/​10.​1016/j.​jcis.​2017.​07.​109
Akhavan F, Montazerb SM (2014) In situ sonosynthesis of nano ­TiO2
determined by in-situ SEM analysis, against E. coli (gram
on cotton fabric. Ultrason Sonochem 21:681–691. https://​doi.​org/​
negative) and B. pumilus (gram positive) was greater for 10.​1016/j.​ultso​nch.​2013.​09.​018
Indiolino cotton. The T ­ iO2-NPs homogeneous distribution Al-Taweel SS, Saud HR (2016) New route for synthesis of pure anatase
on the cotton fabric surface enhance the bactericidal capac- ­TiO2 nanoparticles via ultrasound-assisted sol-gel method. J Chem
Pharm Res 8:620–626
ity which is favored by the sonosynthesis method using Ti
Borsa BA, Aldağ ME, Tunalı B, Dinç U, Güngördü DZ, Özalp VC
isopropoxide as precursor. (2016) A sepsis case caused by a rare opportunistic pathogen:
The results show that, it is feasible the functionalization Bacillus pumilus. Mikrobiyol Bul 50:466–470. https://​doi.​org/​10.​
of cotton fabrics with photoactive ­TiO2-NPs to produce face 5578/​mb.​27575
Botequim D, Maia J, Lino MMF, Lopes LMF, Simões PN, Ilharco
masks with good bactericidal capacity and self-cleaning
LM, Ferreira L (2012) Nanoparticles and surfaces presenting anti-
properties. fungal, antibacterial and antiviral properties. Langmuir 28:7646–
7656. https://​doi.​org/​10.​1021/​la300​948n
Acknowledgements  We thank to H. Fabián Alonso-Cordero (UMAC- Burlacov I, Jirkovský J, Müller M, Heimann RB (2006) Induction
CICESE) for the SEM analysis, and Iván Puente (FQ-UNAM) for the plasma-sprayed photocatalytically active titania coatings and
SEM-EDS analysis. their characterisation by micro-Raman spectroscopy. Surf Coat
Tech 201:255–264. https://d​ oi.o​ rg/1​ 0.1​ 016/j.s​ urfco​ at.2​ 005.1​ 1.1​ 17
Author contributions  Conceptualization: SFM, LCC; LCC, Formal Conti SF, Gettner ME (1962) Electron microscopy of cellular division
análisis: GAN, RDCN, SFM; Funding acquisition: SFM, LCC; Inves- in escherichia coli. J Bacteriol 83:544–550. https://​doi.​org/​10.​
tigation: LCC, VMC, RDCN, KAHH; Methodology: LCC, VMC, 1128/​jb.​83.3.​544-​550.​1962
RDCN, KAHH; Project administration: SFM; Resources: SFM;

13

4032 Applied Nanoscience (2022) 12:4019–4032

Daoud WA, Xin JH (2004) Nucleation and growth of anatase crys- formation, morphology, and antibacterial activity. Surf Coat Tech-
tallites on cotton fabrics at low temperatures. J Am Ceram Soc nol 204:54–57. https://​doi.​org/​10.​1016/j.​surfc​oat.​2009.​06.​028
87:953–955. https://​doi.​org/​10.​1111/j.​1551-​2916.​2004.​00953.x Perelshtein I, Applerot G, Perkas N, Grinblat J, Gedanken A (2012)
Daoud WA, Xin JH, Yi-He Z (2005) Surface functionalization of cel- A one-step process for the antimicrobial finishing of textiles with
lulose fibers with titanium dioxide nanoparticles and their com- crystalline ­TiO2 nanoparticles. Chem Eur J 18:4575–4582. https://​
bined bactericidal activities. Surf Sci 599:69–75. https://​doi.​org/​ doi.​org/​10.​1002/​chem.​20110​1683
10.​1016/j.​susc.​2005.​09.​038 Prasad K, Pinjari DV, Pandit AB, Mhaske ST (2010) Synthesis of tita-
Grutsch AA, Nimmer PS, Pittsley RH, McKillip JL (2018) Bacillus nium dioxide by ultrasound assisted sol–gel technique: Effect of
spp. as Pathogens in the Dairy Industry. In: Holban AM, Grumez- amplitude (power density) variation. Ultrason Sonochem 17:697–
escu AM (eds) Handbook of Food Bioengineering, Foodborne 703. https://​doi.​org/​10.​1016/j.​ultso​nch.​2010.​01.​005
Diseases. Academic Press, Elsevier, pp 193–211 Praveen P, Viruthagiri G, Mugundan S, Shanmugam N (2014) Struc-
Guo W, Lin Z, Wang X, G, (2003) Sonochemical synthesis of nanocrys- tural, optical and morphological analyses of pristine titanium di-
talline ­TiO2 by hydrolysis of titanium alkoxides. Microelectron oxide nanoparticles – Synthesized via sol–gel route. Spectrochim
Eng 66:95–101. https://​doi.​org/​10.​1016/​S0167-​9317(03)​00031-5 Acta Part A 117:622–629. https://​doi.​org/​10.​1016/j.​saa.​2013.​09.​
Hadad L, Perkas N, Gofer Y, Calderon-Moreno J, Ghule A, Gedanken 037
A (2007) Sonochemical deposition of silver nanoparticles on wool Qina X, Jing L, Tian G, Qu Y, Feng Y (2009) Enhanced photocata-
fibers. J Appl Polym Sci 104:1732–1737. https://​doi.​org/​10.​1002/​ lytic activity for degrading Rhodamine B solution of commer-
app.​25813 cial Degussa P25 TiO2 and its mechanisms. J Hazard Mater
Hana E, Vijayarangamuthu K, Youn J, Parkb Y, Jung S, Jeon K (2018) 172:1168–1174. https://​doi.​org/​10.​1016/j.​jhazm​at.​2009.​07.​120
Degussa P25 TiO2 modified with H2O2 under microwave treat- Senić Ž, Bauk S, Vitorović-Todorović M, Pajić N, Samolov A, Rajić
ment to enhance photocatalytic properties. Catal Today 303:305– D (2011) Application of ­TiO2 nanoparticles for obtaining self
312. https://​doi.​org/​10.​1016/j.​cattod.​2017.​08.​057 decontaminating smart textiles. Sci Tech Rev 61:63–72
Hosseini-Sarvari M, Jafari F, Abdulhamid D (2022) The study of Singhal S, Khanna P, Khanna L (2021) Synthesis, comparative in vitro
TiO2/Cu2O nanoparticles as an efcient nanophotocalyst toward antibacterial, antioxidant and UV fluorescence studies of bis
surface adsorption and photocatalytic degradation of methyl- indole Schiff bases and molecular docking with ct-DNA and
ene blue. Appl Nanosci 12:2195–2205. https://​doi.​org/​10.​1007/​ SARS-CoV-2 ­Mpro. Luminescence 36:1531–1543
s13204-​022-​02474-x Skiba M, Vorobyova V (2020) Synthesis OF AG/TIO2 nanocomposite
Hussain CM (2020) Handbook of nanomaterials for manufacturing via plasma liquid interactions and degradation methylene blue.
applications. Elsevier Appl Nanosci 10:4717–4723
Konda A, Prakash A, Moss GA, Schmoldt M, Grant GD, Guha S Uddin MJ, Cesano F, Bonino F, Bordiga S, Spoto G, Scarano D, Zec-
(2020) Aerosol filtration efficiency of common fabrics used in china A (2007) Photoactive T ­ iO2 films on cellulose fibres: syn-
respiratory cloth masks. ACS Nano 14:6339–6347. https://​doi.​ thesis and characterization. J Photoch Photobio A 189:286–294.
org/​10.​1021/​acsna​no.​0c032​52 https://​doi.​org/​10.​1016/j.​jphot​ochem.​2007.​02.​015
Lessan F, Montazer M, Moghadam MB (2011) A novel durable flame- Ugur SS, Sarusik M, Aktas H (2010) The fabrication of nanocomposite
retardant cotton fabric using sodium hypophosphite, nano T ­ iO2 thin films with ­TiO2 nanoparticles by the layer-by-layer deposi-
and maleic acid. Thermochim Acta 250:48–54. https://d​ oi.o​ rg/1​ 0.​ tion method for multifunctional cotton fabrics. Nanotechnology
1016/j.​tca.​2011.​03.​012 21:325603. https://​doi.​org/​10.​1088/​0957-​4484/​21/​32/​325603
Militky J, Novak O, Kremenakova D, Wiener J, Venkataraman M, Zhu Wu Y, Hong-Mei L, Bo-Qing X, Zao-Li Z, Dang-Sheng S (2007) Sin-
G, Yao J, Aneja A (2021) A review of impact of textile research gle-phase titania nanocrystallites and nanofibers from titanium
on protective face masks. Materials 14:1937. https://​doi.​org/​10.​ tetrachloride in acetone and other ketones. Inorg Chem 46:5093–
3390/​ma140​81937 5099. https://​doi.​org/​10.​1021/​ic070​199h
Montazer M, Seifollahzadeh S (2011) Enhanced self-cleaning, antibac- Yaqoob AA, Umar K, Ibrahim MNM (2020) Silver nanoparticles: vari-
terial and UV protection properties of nano ­TiO2 treated textile ous methods of synthesis, size afecting factors and their potential
through enzymatic pretreatment. Photochem Photobiol 87:877. applications–a review. Appl Nanosci 10:1369–1378. https://​doi.​
https://​doi.​org/​10.​1111/j.​1751-​1097.​2011.​00917.x org/​10.​1007/​s13204-​020-​01318-w
Ogunsona EO, Muthuraj R, Ojogbo E, Valerio O, Mekonnena TH Yocupicio-Gaxiola RI, Petranovskii V, Sánchez P, Antúnez-García J,
(2020) Engineered nanomaterials for antimicrobial applications: Alonso-Núñez G, Galván DH, Murrieta-Rico FN (2021) Prospects
A review. Appl Mater Today 18:100473. https://d​ oi.o​ rg/1​ 0.1​ 016/j.​ for further development of face masks to minimize pandemics –
apmt.​2019.​100473 functionalization of textile materials with biocide inorganic nano-
Pakdel E, Daoud WA (2013) Self-cleaning cotton functionalized with particles: a review. IEEE Lat Am Trans 19:1010–1023. https://d​ oi.​
­TiO2/SiO2: Focus on the role of silica. J Colloid Interface Sci org/​10.​1109/​TLA.​2021.​94512​47
401:1–7. https://​doi.​org/​10.​1016/j.​jcis.​2013.​03.​016
Percival SL, Williams DW (2014) Escherichia coli. In: Percival SL, Publisher's Note Springer Nature remains neutral with regard to
Yates MV, Williams DW, Chalmers RM, Gray NF (eds) Micro- jurisdictional claims in published maps and institutional affiliations.
biology of Waterborne Diseases. Elsevier, Academic Press, pp
89–117 Springer Nature or its licensor holds exclusive rights to this article under
Perelshtein I, Applerot G, Perkas N, Wehrschuetz-Sigl E, Hasmann A, a publishing agreement with the author(s) or other rightsholder(s);
Guebitz G, Gedanken A (2009a) Antibacterial properties of an author self-archiving of the accepted manuscript version of this article
in situ generated and simultaneously deposited nanocrystalline is solely governed by the terms of such publishing agreement and
ZnO on fabrics. Appl Mater Inter 1:361–366. https://​doi.​org/​10.​ applicable law.
1021/​am800​0743
Perelshtein I, Applerot G, Perkas N, Wehrschuetz-Sigl E, Hasmann
A, Guebitz G, Gedanken A (2009b) CuO–cotton nanocomposite:

13