Science of the Total Environment 438 (2012) 66–71

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Science of the Total Environment

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

Adsorption of norfloxacin onto titanium oxide: Effect of drug carrier and dissolved
humic acid
Hong Peng a, Shixiang Feng b, Xu Zhang b,⁎, Yan Li b, Xiaoyue Zhang c
a
School of Water Resources and Hydropower, State Key Laboratory of Water Resources and Hydropower Engineering Science, Wuhan University, Wuhan, 430072, P.R. China
b
School of Resources and Environmental Science, Wuhan University, Wuhan, 430079, P.R. China
c
School of Economic and Management, Wuhan University, Wuhan, 430072, P.R. China

H I G H L I G H T S

► Co-effect of drug carriers and humic acid on norfloxacin adsorption on TiO2 is investigated;
► pH and TiO2 surface areas play an important role on norfloxacin adsorption.
► Adsorption is determined based on zeta potential and FT-IR analysis.

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

Article history: Titanium dioxide is widely used as an effective catalyst in wastewater treatment. The effects of drug carriers
Received 28 May 2012 (cyclodextrins, 100 μM) or dissolved humic acids (0–50 mg/L) or pH (3.0–11.0) on adsorption of norfloxacin
Received in revised form 9 August 2012 to two TiO2 (Hombikat UV-100 and Anatase TiO2) surfaces were systematically studied. Norfloxacin shows
Accepted 9 August 2012
high adsorption affinity to TiO2 surface. Specific surface area of TiO2 shows great influence on norfloxacin
Available online 8 September 2012
adsorption especially in acidic solutions. The effect of pH on norfloxacin adsorption originates from the
Keywords:
changes of TiO2's surface charge and speciation of norfloxacin. The presence of humic acids (50 mg/L)
Adsorption suppresses the adsorption of norfloxacin onto Hombikat UV-100 and Anatase TiO2 prominently. The
Cyclodextrin co-effect of heptakis(2,6-di-O-methyl)-β-cyclodextrin (methyl-β-CD) and humic acid is similar to the solo
Humic acid effect of humic acid on the adsorption of norfloxacin onto Hombikat UV-100, while the co-effect shows a
Norfloxacin more retardation effect on the adsorption of norfloxacin onto Anatase TiO2. Humic acid and β-CD show a
TiO2 synergetic depressed effect on the adsorption of norfloxacin onto both TiO2 surfaces. These results show
that both aquatic solution chemistry and drug carrier are important to norfloxacin adsorption on TiO2,
which could alter the environmental fate and transport of norfloxacin.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction nano-sized materials on the environmental fate and transport of

In recent decades, there has been a serious concern over the
environmental risks of nano-sized materials after they are released
to the environment since a large amount of nano-sized materials
are produced and used (Zhu et al., 2010; Xiong et al., 2011; Gerloff
et al., 2012). Because of the small size, nano-sized materials can
enter into cells and cause various damages. Additionally, the
adsorbed pollutants from the aquatic environment would also con-
tribute to the toxicity of nano-sized materials (Colvin, 2003; Yang
et al., 2006). Therefore, it is worthwhile to study the adsorption
properties of toxic chemicals onto nano-sized materials in order to
obtain a better understanding of nano-sized materials' environmen-
tal risk. Moreover, the study is also helpful to uncover the effect of
⁎ Corresponding author. Tel.: +86 27 68772910; fax: +86 27 68778893.
E-mail address: xuzhangwhu@gmail.com (X. Zhang).
various pollutants (Yang et al., 2006; Pan et al., 2008; Ji et al., 2010;
Zhang et al., 2010; Gai et al., 2011; Zhang et al., 2011).
As the most common semiconductor, titanium dioxide (TiO2) has
been widely used as a photocatalyst in the environmental realm. The
photodegradation of various organic pollutants, the photo-reduction
of inorganic contaminants and the inactivation of microorganisms
have been performed with noteworthy results (Chong et al., 2010;
Kurniawan et al., 2011). The degradation of norfloxacin (NFXC), a
typical member of the pharmaceuticals and personal care products
(PPCPs), over TiO2 has been investigated under various conditions
(Haque and Muneer, 2007; Paul et al., 2007; An et al., 2010; Li et al.,
2012). It was suggested that norfloxacin formed a coordination com-
plex with the surface of TiO2, and underwent one electron oxidation
reaction under visible irradiation (Paul et al., 2007). However, the
adsorption of norfloxacin onto TiO2 has not been systematically
studied yet including the effect of pH, specific surface area of cata-
lysts, and concentration of dissolved organic matter (e.g. humic acid).

0048-9697/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.scitotenv.2012.08.045
 H. Peng et al. / Science of the Total Environment 438 (2012) 66–71
It is well known that aquatic environment conditions usually show
great influence on the fate and transport of pollutants (Yamamoto et
al., 2003; Yang and Xing, 2009; Ge et al., 2010; Maoz and Chefetz,
2010). On the other side, many kinds of drug carriers including cyclo-
dextrins, surfactants, other amphiphiles, etc. are widely used in phar-
maceutical products to improve the delivery and the effectiveness of
drugs (Szejtli, 2004; Uekama, 2006; Zhou et al., 2010; Jazkewitsch et
al., 2011; Yhaya et al., 2011). Although drug carriers found in the envi-
ronment are likely to be present at low concentrations and are usually
not regarded as contaminants, drug carriers released to the environ-
ment with PPCPs will likely be present at relatively higher concentra-
tions than PPCPs themselves (Hari et al., 2005). It was found that the
fate and transport of host–guest supramolecules are different from
that of free guests (Sortino et al., 2001; Allan et al., 2007; Wang et al.,
2007) and the adsorption/desorption process of pollutants also changed
in the presence of drug carriers as well as dissolved organic matter.
The influence of cyclodextrins (β-cyclodextrin and methyl-β-
cyclodextrin), dissolved organic matter (humic acid concentrations)
and pH on the adsorption of norfloxacin to two TiO2 were investigat-
ed in this work. The objectives of this work were to determine the ex-
tent to which adsorption was influenced by varying drug carriers,
aquatic environment conditions, the ionization state of norfloxacin
and surface properties of nano-sized materials.
2. Materials and methods
2.1. Chemicals
Norfloxacin (98+%) was purchased from Tokyo Chemical Industry
and used as received. Commercial humic acid (Sigma-Aldrich, sodium
salt) was purified before use according to a previous work (Cho and
Choi, 2002). Typically, humic acid (HA) was initially dissolved in a
pH 12 aqueous solution at 500 mg/L, and then the solution was
acidified to pH 3. The undissolved HA was removed by a 0.45 μm
nylon membrane filter and the purified HA was recovered by vacuum
freeze drying. β-Cyclodextrin (Scheme 1) was a commercial product of
the Sinopharm Chemical Reagent Co. Ltd. (Shanghai, China), and
heptakis(2,6-di-O-methyl)-β-cyclodextrin (methyl-β-CD) was obtained
from Aladdin-reagent Corporation (Shanghai, China). Hombikat UV-100
and Anatase TiO2 were either directly purchased from the manufacturer
Scheme 1. Structures of β-cyclodextrin, methyl-β-cyclodextrin, and norfloxacin.
67
or obtained from distributors and used as the photocatalyst. Deionized
water (resistivity>18.0 MΩ cm) was used during sample preparation.
Norfloxacin (100 μM), humic acid sodium (100 mg/L), β-CD
(1 mM) and methyl-β-CD (1 mM) stock solutions were prepared by
dissolving solid compounds in water. All solutions at lower concen-
trations were prepared by dilution. 1 g/L TiO2 was prepared by direct-
ly adding 0.05 g TiO2 in to 50 ml solutions containing analyte.
2.2. Characterization of TiO2 used in this work
The Brunauer–Emmett–Teller surface area was determined using a
Gemini V 2380 instrument. The X-ray diffraction (XRD) patterns of the
prepared products were recorded on a Dmax-rA powder diffractometer
(Rigaku, Japan) using Cu Kα radiation and a step width of 2θ=0.02°.
High resolution transmission electron microscopy images were obtained
on a JEOL JEM 2010FEF microscope (Japan Electronics, Japan) using an
accelerating voltage of 200 kV. The diameters of TiO2 particles were de-
termined from the statistical analysis of the TEM image. The physical
properties of TiO2 are listed in Table 1.
2.3. FT-IR study of adsorption of norfloxacin onto TiO2
The adsorption of norfloxacin onto TiO2 was characterized by FT-IR
spectroscopic measurement. Norfloxacin (20 μM) was added to aque-
ous TiO2 dispersion (1 g/L) and stirred for 2 h. Norfloxacin-adsorbed
TiO2 powder was recovered by centrifuging the suspension and drying
in an vacuum oven at 60 °C overnight. FT-IR spectra of sample pellets
with KBr were recorded on a Fourier transform infrared (FTIR) spec-
trometer Nicolet 5700 (Thermo Electron Corporation, American).
2.4. Equipments and methods
The concentrations of norfloxacin were determined using the
reversed-phase HPLC method. The experiments were performed using
a Waters 484 HPLC with an Agilent Zorbax SB-C18 column (5 μm,
4.6 × 250 mm). The mobile phase was a 0.025 mol/L phosphoric
acid-acetonitrile (80/20, V/V) mixed solution (pH 3.0, adjusted with
triethylamine) with a flow rate of 1.0 ml/min. The UV detection wave-
length was set at 278 nm. The retention time for norfloxacin was
3.8 min and its concentration was determined by working curve
68 H. Peng et al. / Science of the Total Environment 438 (2012) 66–71

Table 1
Physical properties of TiO2 used in this study.

Catalysts Crystalline form (%) TEM diameter BET

(nm)a (m2/g)
Anatase Rutile

Hombikat UV-100 100 0 8±2 249

Anatase TiO2 100 0 12 ± 3 96
a
The diameter was analyzed based on the statistic analysis method by using
DigitalMicrography software.

method from 0.1 μmol/L to 100 μmol/L. The concentration of cyclodex-

trin was determined from the total organic carbon (TOC) data, which
were recorded on an Anlytik Jena AG Multi N/C 2100 TOC/TN
instrument. The zeta potential of TiO2 in the presence and in the ab-
sence of norfloxacin was determined using a ZetaSizer 3600 (Malvern
Instrument).
The adsorption studies were performed in the dark using aqueous
suspensions containing 1–50 μM of norfloxacin and 1.0 g/L of TiO2.
The 50 ml suspension in the 100 ml glass vessels was continuously
stirred by using constant temperature magnetic stirrer for 12 h. The
tests on the effects of β-CD, methyl-β-CD and humic acid on the
adsorption of norfloxacin were performed in the same way. Langmuir
isotherms were used to quantify the adsorption of norfloxacin onto
TiO2. KL and qmax were determined from a nonlinear regression fit of
the Langmuir equation (Eq. (1)):

Fig. 1. Dependence of norfloxacin bulk concentration (ct) with contact time and cyclo-
q max K L ce
qe ¼ ð1Þ dextrins (100 μM) in 1 g/L TiO2 suspension, inset: adsorption kinetics of norfloxacin to
1 þ K L ce TiO2, and the lines correspond to the fits of the data to the pseudo‐second-order kinetic
mode (qt represents the adsorption amount of norfloxacin per gram TiO2 at different
where qe (μmol/g) is the amount of solute adsorbed per gram of TiO2, time intervals). cNFXC = 1 μM.

KL(L/mol) is the Langmuir equilibrium constant, qmax is the maximum

adsorption capacity of the solute on the TiO2 surface and ce (μM) is The correlation coefficient (r 2) for the pseudo second-order kinet-
equilibrium concentration of solute. ic model is higher than 0.999, which suggests that the pseudo
The rate (R, %) for the adsorption of norfloxacin onto TiO2 was cal- second-order model is a good approach for describing the adsorption
culated from Eq. (2): process of norfloxacin to TiO2. The adsorption kinetic constants are
not changed in the presence of either 100 μM β-CD or methyl-β-CD.
ct
R¼  100% ð2Þ
c0 3.2. Effect of pH on the adsorption of norfloxacin

where c0 and ct represent the initial concentration and the concentra-
tion at different time intervals, respectively.
All the experiments were performed in triplet and described as
mean ± stand deviation. The regression of the experimental data
was carried out by using Origin 7.5 software.
3. Results and discussion
3.1. Adsorption equilibrium of norfloxacin onto TiO2
Adsorption experiments using an initial concentration of 1 μmol/L
were used to determine adsorption rates in order to evaluate the
effect of pH on adsorption of norfloxacin. Adsorption studies of
norfloxacin to TiO2 were studied for pH ranging from 3.0 to 11.0
and the results are shown in Fig. 2. The adsorption rates are relatively
smaller in acidic solutions for the adsorption of norfloxacin onto TiO2
and increased quickly with the increase of pH. The positively charged
form is the dominant species for norfloxacin at pH below 6.2 while
the zwitterionic form was dominant between 6.2 and 8.0, and the

As listed in Table 1, the selected nano-sized TiO2 has a narrow

range of particle size, but the specific surface area is quite different
from each other. Equilibrium sorption studies were firstly inves-
tigated with two sorbents in the presence and in the absence of
cyclodextrins.
The influences of contact time on the adsorption of norfloxacin onto
TiO2 are illustrated in Fig. 1. The bulk concentration of norfloxacin
decreased quickly with time up to 10 min and then reached equilibrium
in 60 min for both TiO2. The adsorption rate increases with the increase
of TiO2's specific surface area. The presence of 100 μM β-CD or 100 μM
methyl-β-CD hardly shows any influence on the adsorption equilibrium
of norfloxacin. The results are not unexpected because norfloxacin can
form a coordination complex with the surface of TiO2 (Paul et al.,
2007), which suggests that forming the host–guest inclusion complex
is likely not a major factor in the adsorption of norfloxacin in the Fig. 2. Dependence of norfloxacin adsorption rate (R, %) over Hombikat UV-100 (■),
presence of cyclodextrins. Anatase TiO2 (●), and existing norfloxacin form with solution pH.
 H. Peng et al. / Science of the Total Environment 438 (2012) 66–71
anionic form only exists at pH higher than 6.5 according to its acid–
base equilibrium constant (Ross and Riley, 1990). The adsorption to
Anatase TiO2 starts to increase at pH 4.0 at which the fraction of the
zwitterionic form of norfloxacin starts to increase. The adsorption
rate increases to the peak point around pH 9.5, at which the anionic
form of norfloxacin becomes the predominant species. The adsorp-
tion on Hombikat UV-100 reached the maximum point at pH of
about 4.5 which followed in the cationic region of norfloxacin.
Compared with the adsorption of norfloxacin onto Anatase TiO2, the
relatively higher adsorption rates onto Hombikat UV-100 is caused
by Hombikat UV-100's larger specific surface area. The adsorption of
norfloxacin onto both TiO2 surfaces decreases sharply when the pH
ranges from 9.5 to 10.5.
The zeta potential values were measured in 0.1 M NaCl solutions
in order to investigate the mechanism of adsorption of norfloxacin
to TiO2. The values of zeta potential as a function of pH are shown
in Fig. 3. The points of zero charges (PZC) for Hombikat UV-100 and
Anatase TiO2 are 6.1 and 6.0, respectively. The adsorption of NFXC
on TiO2 shifts the negative zeta potential to positive, which suggests
the surface complex formation between norfloxacin and TiO2. The
results indicate that the adsorption is likely to occur by covalent
bond formation.
3.3. FT-IR study of norfloxacin to TiO2
FT-IR spectra of norfloxacin and norfloxacin-adsorbed TiO2 are
shown in Fig. 4. The FT-IR spectrum of norfloxacin has been well
assigned (Sadeek, 2005). The adsorption peaks centered at 1730
and 1621 cm −1 were assigned as the υ(C_O) stretching vibration
of the carboxylic group and υ(C_O) stretching vibration of
pyridine-keto, respectively. The υ(C_O) stretching vibration of the
carboxylic group observed at 1730 cm −1 for norfloxacin disappeared
after adsorption, which indicates the involvement of the carboxyl
group in the interaction with TiO2. Therefore, the possible bonding
mode for norfloxacin–TiO2 is bidentate through the carboxylate li-
gand (inset figure in Fig. 4). The results are similar with several
norfloxacin metal ion complexes (Sadeek, 2005; Chattah et al.,
2007; Shaikh et al., 2007; Khallow and Al-Assaf, 2011).
3.4. Isotherms for adsorption of norfloxacin to TiO2
Dependence of the adsorption amount with the equilibrium concen-
tration of norfloxacin and cyclodextrins onto TiO2 were shown in Figs. 5
and 6. The results show that the adsorbed norfloxacin over Hombikat
UV-100 increased more sharply than those over Anatase TiO2 because
of the relatively larger specific surface area. The lines depicted in
Figs. 5 and 6 show the plots of adsorption experimental data fitted
with Langmuir adsorption isotherms. The fitted parameters of adsorp-
tion equations were listed in Table 2.
Fig. 3. Zeta potential of suspended TiO2 particle in the presence of 0.1 M NaCl as a function
of pH, cNFXC =20 μM, TiO2 =0.1 g/L.
69
Fig. 4. FT-IR spectra of free norfloxacin, norfloxacin-adsorbed TiO2, inset: possible
mode for the adsorption of norfloxacin onto the TiO2 surface.
KL (L/mol) for the adsorption of norfloxacin in the absence of any
cyclodextrins on Hombikat UV-100 and Anatase TiO2 are 0.94 ±
(0.25) × 10 6 and 0.47 ± (0.06) × 10 6, respectively. The obtained KL
values are quite larger than the values (10 4–10 5 L/mol) reported for
norfloxacin attached to some other adsorbents (Hari et al., 2005;
Zhang and Dong, 2008; Zhang et al., 2009; Yang et al., 2012). The cal-
culated maximum adsorption amount (μmol/g) for adsorption of
norfloxacin onto Hombikat UV-100 and Anatase TiO2 are respectively
found to be 89.3 ± 8.4, and 33.0 ± 1.2.
The presence of 100 μmol/L β-CD shows a moderate effect on the
adsorption over either Hombikat UV-100 or Anatase. The adsorption
constant for the adsorption of β-CD on Hombikat UV-100 and Anatase
TiO2 are found to be 4.0 × 10 4, and 2.6 × 10 4 L/mol, respectively. The
results showed that β-CD had a much smaller adsorption affinity
than the adsorption of norfloxacin onto Hombikat UV-100 and
Anatase TiO2. It was suggested that the hydroxyl group played an
important role in adsorption onto the TiO2 surface (Tachikawa et al.,
2004). Because all of the hydroxyl groups at C2 and C6 were
substituted by methyl groups, methyl-β-CD has minimal adsorption
onto the TiO2 surface (Fig. 7). Therefore, forming inclusion complexes
with methyl-β-CD would decrease the adsorption of norfloxacin to
some extent.
3.5. Co-effect of humic acid and cyclodextrins on the adsorption of
norfloxacin
It is evident in Fig. 8 that the presence of humic acid showed a re-
duced effect on the adsorption of norfloxacin. Humic acid (50 mg/L)
decreases norfloxacin adsorption on Hombikat UV-100 and Anatase
TiO2 markedly, up to about 30% and 35%, respectively. The various
structural components in humic acids are expected to interact
Fig. 5. Dependence of the adsorbed norfloxacin per gram Anatase TiO2 (qe) with the
equilibrium concentration (ce) and cyclodextrins (100 μM). The solid lines correspond
to the fits of the data to the Langmuir adsorption isotherm model.
70 H. Peng et al. / Science of the Total Environment 438 (2012) 66–71

Fig. 6. Dependence of the adsorbed norfloxacin per gram Hombikat UV-100 (qe) with Fig. 7. Dependence of the adsorbed β-CD and methyl-β-CD over different TiO2 (qe)
the equilibrium concentration (ce) and cyclodextrins (100 μM). The solid lines corre- with the equilibrium concentration (ce). The solid lines correspond to the fits of the
spond to the fits of the data to the Langmuir adsorption isotherm model. data to the Langmuir adsorption isotherm model.

strongly with the surface of TiO2 through different interactions in-
cluding van der Waals forces, π–π electron coupling, H-bonding and
surface complex. (Yang and Xing, 2009; Ji et al., 2010). It was reported
that a HA molecule would occupy approximately 20 nm 2 on the TiO2
surface assuming a molar mass of 4000 (Enriquez and Pichat, 2001).
Therefore, the dissolved humic acids show high adsorption affinity
to TiO2 resulting in a competitive effect on norfloxacin adsorption.
The co-effect of humic acid and methyl-β-CD is similar to the solo
effect of humic acid on the adsorption of norfloxacin onto Hombikat
UV-100, while the co-effect shows more retardation effect than the
solo effect of humic acid on the adsorption of norfloxacin onto
Anatase TiO2. Humic acid and β-CD show a synergetic depressed ef-
fect on norfloxacin adsorption. The decrease of norfloxacin adsorp-
tion in the presence of 50 mg/L humic acid and 100 μmol/L β-CD on
Hombikat UV-100 and Anatase TiO2 is up to about 38% and 46%,
respectively.
3.6. Significance for environmental fate of norfloxacin
nanoparticles to some extent because of their retardation effect on
the adsorption of norfloxacin. On the other side, since visible light
induced degradation of norfloxacin occurred over the surface of
TiO2 (Paul et al., 2007), its environmental transport and fate could
also be changed remarkably in the presence of cyclodextrins and
humic acid since the adsorption properties could alter.
4. Conclusions
The results obtained in the present study indicate that dissolved
organic matter (humic acid), drug carriers (cyclodextrins) and
solution pH play an important role in norfloxacin adsorption on
TiO2 surface. Norfloxacin adsorption on TiO2 surface is highly
pH-dependent especially for TiO2 with a small specific surface area.
Dissolved humic acids (50 mg/L) inhibit norfloxacin adsorption on
Hombikat UV-100 and Anatase TiO2 prominently. Humic acid and
β-CD show a synergetic depressed effect on norfloxacin adsorption.
In addition to the potential application of TiO2 as catalysts in

The results of this work indicate that cyclodextrins slightly influ-

ence the adsorption of norfloxacin onto TiO2, potentially decreasing
its mobility accompanied with nanoparticles. The results are to
some extent consistent with the effect of surfactants (Hari et al.,
2005). It was suggested that the surface of nanoparticles would be
coated with dissolved organic matter, and hence increase the adsorp-
tion of hydrophobic organic compounds (Wang et al., 2008; Yang and
Xing, 2009). The pollutants studied in the previous study were like
pyrene and phenanthrene, which have high affinity to dissolved
organic matter and low affinity to nanoparticles (Wang et al., 2008;
Wang et al., 2011). However, dissolved organic matter, like humic
acid in this work, showed a great retardation effect on the adsorption
of NFXC to TiO2 either in the presence or in the absence of cyclodex-
trins. Hence, dissolved humic acid could reduce additional toxicity of

Table 2
Calculated Langmuir equilibrium constant (KL(±SD), L/mol), maximum adsorption capac-
ity (qmax(±SD), μmol/g) and the correlation coefficient square (R2) for the adsorption of
NFXC in the absence and in the presence of cyclodextrins on TiO2.

Adsorbents Adsorbates qmax KL/106 R2

(μmol/g) (L/mol)

Hombikat NFXC 89.3 ± 8.4 0.94 ± 0.25 0.987

UV-100 NFXC+ 100 μM β-CD 94.2 ± 16.1 1.07 ± 0.31 0.982
NFXC+ 100 μM 70.8 ± 11.1 1.13 ± 0.38 0.974
methyl-β-CD
Anatase TiO2 NFXC 33.0 ± 1.2 0.47 ± 0.06 0.994
NFXC+ 100 μM β-CD 31.0 ± 1.3 0.29 ± 0.04 0.993
NFXC+ 100 μM 30.0 ± 2.0 0.32 ± 0.06 0.981
Fig. 8. Co-effect of humic acid and cyclodextrins (100 μM) on the adsorption rate (R, %)
methyl-β-CD
of norfloxacin in 1 g/L TiO2 dispersion. cNFXC = 1 μM.
 H. Peng et al. / Science of the Total Environment 438 (2012) 66–71
norfloxacin treatment, the present study implies that the release of
TiO2 to the environment could greatly affect the fate and transport
of norfloxacin that exhibits high adsorption affinity. However, it
should be pointed out that the concentration of TiO2 used in this
work is excessively higher than its concentration in natural aquatic
environment. Ongoing work is investigating batch adsorption studies
at lower concentrations of both norfloxacin and TiO2 to reveal as to
what extent the different adsorption properties can be observed.
Acknowledgments
This work has been supported in part by the National Key Scientific
and Technological Project (Nos. 2009ZX07528-003-02, 2009ZX07528-
003-07), Natural Science Foundation of Hubei Province (2011CDB274)
and the Fundamental Research Funds for the Central Universities (No.
121095).
References
Allan IJ, Semple KT, Hare R, Reid BJ. Cyclodextrin enhanced biodegradation of polycyclic
aromatic hydrocarbons and phenols in contaminated soil slurries. Environ Sci
Technol 2007;41:5498–504.
An TC, Yang H, Song WH, Li GY, Luo HY, Cooper WJ. Mechanistic considerations for the
advanced oxidation treatment of fluoroquinolone pharmaceutical compounds
using TiO2 heterogeneous catalysis. J Phys Chem A 2010;114:2569–75.
Chattah AK, Linck YG, Monti GA, Levstein PR, Breda SA, Manzo RH, et al. NMR and IR
characterization of the aluminium complexes of norfloxacin and ciprofloxacin
fluoroquinolones. Magn Reson Chem 2007;45:850–9.
Cho Y, Choi W. Visible light-induced reactions of humic acids on TiO2. J Photochem
Photobiol A Chem 2002;148:129–35.
Chong MN, Jin B, Chow CWK, Saint C. Recent developments in photocatalytic water
treatment technology: a review. Water Res 2010;44:2997–3027.
Colvin VL. The potential environmental impact of engineered nanomaterials. Nat
Biotechnol 2003;21:1166–70.
Enriquez R, Pichat P. Interactions of humic acid, quinoline, and TiO2 in water in relation
to quinoline photocatalytic removal. Langmuir 2001;17:6132–7.
Gai K, Shi B, Yan X, Wang D. Effect of dispersion on adsorption of atrazine by aqueous
suspensions of fullerenes. Environ Sci Technol 2011;45:5959–65.
Ge L, Chen J, Wei X, Zhang S, Qiao X, Cai X, et al. Aquatic photochemistry of fluoroquin-
olone antibiotics: kinetics, pathways, and multivariate effects of main water
constituents. Environ Sci Technol 2010;44:2400–5.
Gerloff K, Fenoglio I, Carella E, Kolling J, Albrecht C, Boots AW, et al. Distinctive toxicity
of TiO2 rutile/anatase mixed phase nanoparticles on Caco-2 cells. Chem Res Toxicol
2012;25:646–55.
Haque MM, Muneer M. Photodegradation of norfloxacin in aqueous suspensions of
titanium dioxide. J Hazard Mater 2007;145:51–7.
Hari AC, Paruchuri RA, Sabatini DA, Kibbey TCG. Effects of pH and cationic and nonionic
surfactants on the adsorption of pharmaceuticals to a natural aquifer material.
Environ Sci Technol 2005;39:2592–8.
Jazkewitsch O, Mondrzyk A, Staffel R, Ritter H. Cyclodextrin-modified polyesters from
lactones and from bacteria: an approach to new drug carrier systems. Macromolecules
2011;44:1365–71.
Ji L, Chen W, Bi J, Zheng S, Xu Z, Zhu D, et al. Adsorption of tetracycline on single-walled
and multi-walled carbon nanotubes as affected by aqueous solution chemistry.
Environ Toxicol Chem 2010;29:2713–9.
Khallow KI, Al-Assaf AYR. Synthesis and characterization of oxozirconium (IV),
dioxomolybdenum (VI) and dioxotungsten (VI) with ciprofloxacin and norfloxacin
complexes. Chem Eur J 2011;8:576–80.
Kurniawan TA, Sillanpää MET, Sillanpää M. Nanoadsorbents for remediation of aquatic
environment: local and practical solutions for global water pollution problems. Crit
Rev Env Sci Technol 2011;42:1233–95.
71
Li W, Guo C, Su B, Xu J. Photodegradation of four fluoroquinolone compounds by titanium
dioxide under simulated solar light irradiation. J Chem Technol Biotechnol 2012;87:
643–50.
Maoz A, Chefetz B. Sorption of the pharmaceuticals carbamazepine and naproxen to
dissolved organic matter: role of structural fractions. Water Res 2010;44:981–9.
Pan B, Lin D, Mashayekhi H, Xing B. Adsorption and hysteresis of bisphenol a and
17α-ethinyl estradiol on carbon nanomaterials. Water Res 2008;42:5480–5.
Paul T, Miller PL, Strathmann TJ. Visible-light-mediated tio2 photocatalysis of fluoro-
quinolone antibacterial agents. Environ Sci Technol 2007;41:4720–7.
Ross DL, Riley CM. Aqueous solubilities of some variously substituted quinolone
antimicrobials. Int J Pharm 1990;63:237–50.
Sadeek SA. Synthesis, thermogravimetric analysis, infrared, electronic and mass spectra
of Mn(II), Co(II) and Fe(III) norfloxacin complexes. J Mol Struct 2005;753:1-12.
Shaikh AR, Giridhar R, Yadav MR. Bismuth-norfloxacin complex: synthesis, physico-
chemical and antimicrobial evaluation. Int J Pharm 2007;332:24–30.
Sortino S, Giuffrida S, Fazio S, Monti S. Spectroscopic characterization and photochem-
ical behavior of host-guest complexes between β-cyclodextrin and drugs
containing a biphenyl-like chromophore. New J Chem 2001;25:707–13.
Szejtli J. Past, present, and future of cyclodextrin research. Pure Appl Chem 2004;76:
1825–45.
Tachikawa T, Tojo S, Fujitsuka M, Majima T. Photocatalytic one-electron oxidation of bi-
phenyl derivatives strongly coupled with the TiO2 surface. Langmuir 2004;20:
2753–9.
Uekama K, Fumitoshi H, Arima H. Pharmaceutical applications of cyclodextrins and
their derivatives. In: Uekama K, editor. Cyclodextrins and their complexes.
Weinheim: WILEY-VCH; 2006. p. 381–422.
Wang GH, Qi PR, Xue XF, Wu F, Deng NS. Photodegradation of bisphenol Z by UV
irradiation in the presence of b-cyclodextrin. Chemosphere 2007;67:762–9.
Wang X, Lu J, Xu M, Xing B. Sorption of pyrene by regular and nanoscaled metal oxide
particles: influence of adsorbed organic matter. Environ Sci Technol 2008;42:
7267–72.
Wang X, Guo X, Yang Y, Tao S, Xing B. Sorption mechanisms of phenanthrene, lindane,
and atrazine with various humic acid fractions from a single soil sample. Environ
Sci Technol 2011;45:2124–30.
Xiong D, Fang T, Yu L, Sima X, Zhu W. Effects of nano-scale TiO2, ZnO and their bulk
counterparts on zebrafish: acute toxicity, oxidative stress and oxidative damage.
Sci Total Environ 2011;409:1444–52.
Yamamoto H, Liljestrand HM, Shimizu Y, Morita M. Effects of physical−chemical
characteristics on the sorption of selected endocrine disruptors by dissolved
organic matter surrogates. Environ Sci Technol 2003;37:2646–57.
Yang K, Xing B. Sorption of phenanthrene by humic acid-coated nanosized TiO2 and
ZnO. Environ Sci Technol 2009;43:1845–51.
Yang K, Zhu L, Xing B. Adsorption of polycyclic aromatic hydrocarbons by carbon
nanomaterials. Environ Sci Technol 2006;40:1855–61.
Yang W, Lu Y, Zheng F, Xue X, Li N, Liu D. Adsorption behavior and mechanisms of
norfloxacin onto porous resins and carbon nanotube. Chem Eng J 2012;179:112–8.
Yhaya F, Lim J, Kim Y, Liang M, Gregory AM, Stenzel MH. Development of micellar novel
drug carrier utilizing temperature-sensitive block copolymers containing cyclo-
dextrin moieties. Macromolecules 2011;44:8433–45.
Zhang J-q, Dong Y-h. Effect of low-molecular-weight organic acids on the adsorption of
norfloxacin in typical variable charge soils of China. J Hazard Mater 2008;151:
833–9.
Zhang J, Li Z, Ge G, Sun W, Liang Y, Wu L. Impacts of soil organic matter, pH and exog-
enous copper on sorption behavior of norfloxacin in three soils. J Environ Sci
2009;21:632–40.
Zhang S, Shao T, Bekaroglu SSK, Karanfil T. Adsorption of synthetic organic chemicals
by carbon nanotubes: effects of background solution chemistry. Water Res
2010;44:2067–74.
Zhang L, Wang L, Zhang P, Kan AT, Chen W, Tomson MB. Facilitated transport of
2,2′,5,5′-polychlorinated biphenyl and phenanthrene by fullerene nanoparticles
through sandy soil columns. Environ Sci Technol 2011;45:1341–8.
Zhou H, Yu W, Guo X, Liu X, Li N, Zhang Y, et al. Synthesis and characterization of
amphiphilic glycidol−chitosan−deoxycholic acid nanoparticles as a drug carrier
for doxorubicin. Biomacromolecules 2010;11:3480–6.
Zhu X, Chang Y, Chen Y. Toxicity and bioaccumulation of TiO2 nanoparticle aggregates
in Daphnia magna. Chemosphere 2010;78:209–15.