Photochemistry and Photobiology, 2014, 90: 1099–1107
Photoactive Titania Float for Disinfection of Water; Evaluation of Cell
Damage by Bioanalytical Techniques
R. Shwetharani, M. S. Jyothi, P. D. Laveena and R. Geetha Balakrishna*
Center for Nano and Material Sciences, Jain University, Ramanagaram, Bangalore, India
Received 9 February 2013, accepted 19 March 2014, DOI: 10.1111/php.12277
ABSTRACT
A photoactive float was fabricated with the modified titania
to cause a feasible disinfection of water, contaminated with
E. coli. The commercially available titania was doped with
neodymium by pulverization technique to enhance its activity
in sunlight and a multiapproach technique was used to evalu-
ate the extended efficiency of the doped sample. X-ray dif-
fraction patterns depicted the retention of anatase phase on
doping and the existence of neodymium was confirmed by
the energy dispersive atomic X-ray analysis and the X-ray
photoelectron spectroscopy. Transmission electron micros-
copy and Bruner–Emmett–Teller analysis depicted a mar-
ginal increase in the particle size and a decrease in the
surface area, respectively. Doping induces semiconductor
behavior with lower band energy that could respond to visi-
ble light and exhibit better disinfection activity. The “f” and
“d” transitions of the lanthanide in doped sample caused
new electronic behavior of trapping/detrapping effect together
with bandgap narrowing. The amount of malondialdehyde,
protein, DNA and RNA released on destruction of E. coli
was observed to be 0.915 3 10
À3
lg mL
À1
, 859.912 lg mL
À1
,
20.173 lg mL
À1
and 1146.073 lg mL
À1
, respectively. The
above analytical methods along with standard plate count
method substantiated the enhanced disinfection efficiency of
the doped sample in sunlight.
INTRODUCTION
The availability of decontaminated water is a serious problem in
rural areas of developing countries. A total of 37.7 million Indi-
ans are affected by waterborne diseases annually, 1.5 million
children are estimated to die of diarrhea and 73 million working
days are lost due to waterborne disease each year (1). The classi-
cal techniques such as ultraviolet light irradiation, ozone treat-
ment, low frequency ultrasonic irradiation and reverse osmosis
processes have their disadvantages and advantages. A simple dis-
infection method which can work in sunlight and without usage
of nonrenewable source of energy is interesting (2). The major
pathogenic organisms responsible for waterborne diseases in
India are bacteria (E. coli, Shigella, V. cholera), viruses (Hepati-
tis A, Poliovirus, Rotavirus) and parasites (E. histolytica, Giardia
Hook worm). E. coli is a gram-negative microorganism and is
used as an indicator organism of fecal contamination. Water-
borne diseases caused from this organism involve flu-like symp-
toms such as diarrhea, nausea, fever and vomiting (3–5). The
present study investigates a feasible and effective method for
inactivation of this pathogenic microbe using a photoactive float.
Titania is a well known photocatalyst for its use in oxidative,
photodestructive and disinfection processes (6). TiO
2
due to its
large band energy absorbs in the near UV and utilizes only a
very small fraction of the solar spectrum and generate excess
electrons in the conduction band and positive holes in the
valence band. At the TiO
2
particle surface, the holes react with
either adsorbed H
2
O or surface OH
À
groups to form HO
.
radicals. Excess electrons in the conduction band react with
molecular oxygen to form superoxide ions, which further
disproportionate to form more HO
.
radicals. Hence, the photocat-
alyst-mediated reactions cause the generation of a number of
reactive oxygen species (ROS) and hydroxyl radicals (HO
.
). The
generated ROS interacts with the cell wall components like pep-
tidoglycan, amino acids and lipids, and causes the damage of the
bacterial cell wall. TiO
2
utilizes only a small fraction of the solar
spectrum and this led to the search of a photocatalyst which
could utilize the most abundant energy source—the sunlight. Sul-
fur and nitrogen have been doped into titania to enhance the
absorption of visible light (7–9). The positive and adverse effects
of doping transition metal ions like Au, Ag and Mo into the
TiO
2
lattice for sunlight-mediated catalytic activity have also
been reported (10–13). The special electronic structure 4f
x
, 5d
y
in lanthanide (Ln) ions, having a redox couple of Ln
n+
/Ln
(nÀ1)+
are able to form labile oxygen vacancy of high mobility of bulk
oxygen species which would result in a dissimilar catalytic prop-
erty and different optical property. This influences the photocata-
lytic activity and photocurrent intensity of Ln
n+
-TiO
2
greatly.
Also Ln
n+
is proposed to replace Ti
4+
inside the octahedral inter-
stitial site to impose an unbalanced charge. Therefore, Ti-O-Ln
bond and the charge imbalance are expected to change the sur-
face chemical state of Ln
n+
- TiO
2
greatly (14). We thus have
investigated the doping effect of inner transition metal, neodym-
ium into TiO
2
by solid state technique to induce changes in its
electronic structure for the effective absorption of a broader spec-
trum of sunlight, which results in a higher amount of reactive
oxygen species for an improved and feasible photoinactivation of
E. coli in sunlight. Different biochemical assays have been used
as analytical tools to measure the extent of antibacterial activity.
Titania and its doped analogues were investigated in powder
form for bactericidal activity with respect to both gram-positive
and gram-negative bacteria (15,16). But the suspended powders
*Corresponding author email: geethabalakrishna@yahoo.co.in (R. Geetha Bala
krishna)
© 2014 The American Society of Photobiology
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