Materials Science and Engineering C 69 (2016) 1075–1080

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Materials Science and Engineering C

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

Antibacterial mesoporous molecular sieves modified with

polymeric N-halamine
Yingfeng Wang a, Lin Li a, Ying Liu a, Xuehong Ren a,⁎, Jie Liang b
a
Key Laboratory of Eco-textiles of Ministry of Education, College of Textiles and Clothing, Jiangnan University, Wuxi, Jiangsu, 214122, China
b
The Education Ministry Key Lab of Resource Chemistry and Shanghai Key Laboratory of Rare Earth Functional Materials, Shanghai Normal University, Shanghai 200234, China

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

Article history: In this research, a new kind of porous N-halamine material with high antibacterial efficacies was prepared. Poly
Received 5 April 2016 [5,5-dimethyl-3-(3′-triethoxysilylpropyl)-hydantoin] (PSPH), an N-halamine precursor, was synthesized and
Received in revised form 22 June 2016 grafted onto the surface of mesoporous molecular sieves (SBA-15). The mesoporous molecular sieves modified
Accepted 7 August 2016
with the N-halamine polymer could be rendered biocidal upon exposure to dilute household bleach. The modi-
Available online 9 August 2016
fied mesoporous molecular sieves were characterized by SEM, TEM, FTIR, XPS, TGA, XRD and BET analysis. It was
Keywords:
found that the PSPH has been successfully grafted on the surface of mesoporous molecular sieves, and the mor-
Mesoporous molecular sieves phology and structure of the modified mesoporous molecular sieves were slightly affected. The N-halamine mod-
N-halamine ified mesoporous molecular sieves showed excellent antibacterial property, and inactivated 100% of S. aureus and
Organosilane E. coli O157:H7 with 8.05 and 7.92 log reductions within 1 min of contact, respectively. The modified SBA-15 with
Antibacterial high-antibacterial efficiency has potential application in water treatment and biomaterials areas.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction reacted with γ-chloropropyltriethoxysilane to produce N-halamine pre-

With the increasing in the living standard and awareness of health
and hygiene over the recent years, much more attention has been
aroused to decrease the spread of pathogenic bacteria in various areas,
such as public health, textile materials, medical devices, and air purifica-
tion system [1–3]. For the inactivation of pathogenic bacteria and
protection of people's health, some kinds of antimicrobial
organic agents, such as chitosans [4–6], quaternary ammonium salt [7]
and N-halamines [8–10] have been widely investigated in the
worldwide. N-halamine compounds, containing nitrogen-halogen co-
valent bonds (N-X), were usually formed by the halogenation of
amine, amide or imide groups [11–13]. The antibacterial mechanism
of N-halamine was reported by transferring oxidative chlorine from
N-halamine to bacteria cell membrane and then inactivating the micro-
organism [11,14,15]. The antibacterial efficacies are related to the stabil-
ity of nitrogen-halogen bonds. The stability of N-halamine compounds
follow the order of imide, amide, and amine, whereas the antibacterial
efficacies were in the reverse order [15]. Due to good antibacterial prop-
erties, broad-spectrum against bacteria, eco-friendly and excellent
rechargeability with household bleach solution, N-halamine com-
pounds have been proved to be ideal candidates as antimicrobial agents,
which were used in various material surfaces such as cotton, nylon, paint,
and silica gel [9,16–19]. In this study, 5,5-Dimethylhydantoin sodium salt
⁎ Corresponding author at: Jiangnan University, 214122 Wuxi, China.
E-mail address: xhren@jiangnan.edu.cn (X. Ren).
cursor. The ethyoxyl of organosilane structure in N-halamine
precursor monomer can be hydrolyzed to silanol in water solution.
Then, the N-halamine polymeric precursor was obtained by hydro-
gen adsorption and further dehydration of hydroxy bond of silanol
in the monomer.
Mesoporous molecular sieves are nanoparticles with highly ordered
arrays of one or three dimensional channels and narrow pore size distri-
bution [20], and can be obtained by surfactant-templated synthesis.
Originally, these materials were used as catalysts [21], adsorbents [22]
and hemostatic [23] in many areas. Mesoporous molecular sieves can
be modified with chemicals like siloxanes because of the existence of
functional group (Si\\OH). Organosilane coupling agents [24–26] in-
cluding aminopropyltrimethoxysilane, 3-methacryloxypropyltrime
thoxysilane and chloropropyltriethoxysilane were widely used as
surface modification agents. The covalent bond between organsilane
agents and mesoporous molecular sieves was formed by the
dehydration of hydroxy bond, which make it possible to give functional
properties to the mesoporous molecular sieves after the modification
with silane coupling agents. The mesoporous molecular sieves are
known to have large surface area, huge pore volume, porous structure,
excellent thermal stability and nanometer-size, which make
them have potential in preparing antibacterial materials with good
efficiency [27]. Meanwhile, there has been little information about the
N-halamine antibacterial material based on mesoporous molecular
sieves.
The aim of this work was to obtain antibacterial mesoporous molec-
ular sieves with high efficiencies. In this study, an N-halamine precursor

http://dx.doi.org/10.1016/j.msec.2016.08.017
0928-4931/© 2016 Elsevier B.V. All rights reserved.
1076 Y. Wang et al. / Materials Science and Engineering C 69 (2016) 1075–1080
was synthesized and attached onto the surface of mesoporous molecu-
lar sieves and the schematic of the modification was shown in Scheme 1.
Compared to other support materials, modified mesoporous molecular
sieves with high surface area and pore volume would achieve much bet-
ter antibacterial property and make them possible for antibacterial ad-
sorbents materials or any biomaterials. FT-IR, XPS, SEM, TEM, XRD,
TGA, and BET were used to investigate the microstructure and chemical
structure of the samples. After exposure to dilute bleaching solution, the
modified mesoporous molecular sieves showed excellent antibacterial
efficacies against S. aureus (ATCC 6538) and E. coli O157:H7 (ATCC
43895).
2. Experimental
2.1. Materials
Mesoporous molecular sieves (SBA-15) were purchased from
Nanjing XFNANO Materials Tech Co., Ltd. γ-Chloropropyltriethoxysilane
was supported by J&K Scientific Co., Ltd. 5,5-Dimethylhydantoin was
purchased from Hebei Yaguang Fine Chemical Co., Ltd. Other chemicals
were obtained from Sinopharm Chemical Reagent Co., Ltd. All these re-
agents were used as received without any further purification.
Scheme 1. Schematic illustration of the modification process of SBA-15.
2.2. Pretreatment of SBA-15
In order to enhance the grafting degree of PSPH, dilute hydrochloric
acid was used to activate the hydroxy on the surface of SBA-15. The pre-
treatment of SBA-15 was prepared as follows: In brief, 1.0 g of SBA-15
was acidized for 30 min with 200 mL of 0.1 N hydrochloric acid under
ultrasonic condition. The acidized SBA-15 was centrifugated and then
dried at 110 °C for 24 h under vacuum.
2.3. Synthesis of PSPH
Synthesis of PSPH was performed as the previously described in the
literature [28]. Briefly, 0.1 mol of 5,5-dimethylhydantoin and 0.1 mol of
sodium hydroxide were dissolved in 100 mL of ethanol. The mixture
was refluxed for 10 min, and the organic salt was recovered by drying
at 45 °C for 2 days under vacuum after the solvent was removed
under reduced pressure. After the organic salt was dissolved in DMF,
0.1 mol of γ-chloropropyltriethoxysilane was added into the solution
and stirred for 16 h at 95 °C under N2 protection. The monomer of 5,5-
dimethyl-3-(3′-triethoxysilylpropyl) hydantoin (SPH) was collected
after removal of sodium chloride and solvent by filtration and reduced
pressure distillation. SPH was added into 54 mL water/alcohol (v/v,
2:1) (pH was adjusted to 3.5–5.5 by 0.1 N hydrochloric acid) and the
 Y. Wang et al. / Materials Science and Engineering C 69 (2016) 1075–1080
mixture was refluxed for 6 h at 80 °C. PSPH was obtained from removal
of solvent by heating.
2.4. Modification of SBA-15
A mixture of 1.0 g PSPH, 20 mL alcohol, and 30 mL 0.1 N sodium hy-
droxide solution was stirred for 30 min at room temperature until PSPH
was dissolved in the solvent. Then 1.0 g pretreated SBA-15 was added
into the above solution. The mixture was stirred for 6 h at 78 °C, follow-
ed by the removal of the solvent by heating. The solid product was cured
at 150 °C for 3 min. The modified SBA-15 (SBA-15-PSPH) was obtained
by successive centrifugation with deionized water and alcohol respec-
tively (10,000 rpm, 15 min).
2.5. Chlorination and analytical titration
The modified SBA-15 was chlorinated by soaking in 10% sodium hy-
pochlorite solution at pH = 7 (adjusted with 1 N H2SO4) for 2 h under
room temperature. The chlorinated sample was washed with deionized
water and centrifugated for several times (10,000 rpm, 15 min), and
then dried for 2 h at 55 °C to remove any free non-bonded chorine
absorbed on the samples. The loaded chlorine concentration on the
sample was measured by the standard iodometric/thiosulfate titration.
The amount of chlorine (wt%) for the sample was calculated by the
equation as below:
þ N  V  35:45
Cl ð%Þ ¼  100
W2
Where N and V are the normality (equiv/L) and volume (L) of thio-
sulfate titration, respectively, and W is the weight (g) of the sample.
Fig. 1. TEM images of (a) SBA-15, (b) modified SBA-15, and SEM images of (c) SBA-15, (d) modified SBA-15.
1077
2.6. Antibacterial testing
SBA-15-PSPH and the chlorinated SBA-15-PSPH were used to chal-
lenge with Gram-positive S. aureus (ATCC 6538) and Gram-negative E.
coli O157:H7 (ATCC 43895) for antibacterial efficacy analysis. Firstly,
0.1 g sample was ultrasonic dispersed in 10 mL PBS (phosphate buffer
saline) buffer solution, then a certain amount of bacterial solution was
added to the suspension solution. After contact times of 1, 5, 10, and
30 min, 0.5 mL suspension solution was taken out and mixed with
4.5 mL phosphate buffer solution and sodium thiosulfate solution (v/v,
8:1). The resulting mixture was serially diluted and 100 μL of each dilu-
tion was dispersed onto trypticase agar plates. Colonies on the plates
were counted after incubation at 37 °C for 24 h. The antibacterial effica-
cy of sample was reflected by the CFU of bacteria.
2.7. Characterization
FTIR spectra were recorded at room temperature with Thermo
iS5(Nicolet Instrument Corporation, USA) with KBr pellet method using a
spectral width ranging from 400 to 4000 cm−1 with 4 cm−1 resolution
and an accumulation of 30 scans. SEM images were taken with TM3030
(Hitachi, Japan) scanning electron microscope at 15 kV. TEM images of ze-
olite particles were obtained using JEM-2100 (HR) Transmission Electron
Microscope (JEOL Ltd., Japan) at 200 kV. X-ray powder diffraction patterns
(XRD) of particles were recorded with D8 Advance X-ray diffractometer
(Brucker, Germany) at 3 kW with Cu Kα radiation (λ = 0.154 nm) in the
range of 0.5–5° and 10–70° with a step of 0.02°. X-ray photoelectron spec-
troscopy (XPS) was collected using ESCLAB 250Xi (Thermo Scientific, USA)
with Al K radiation (energy step size was 0.05 eV). Thermogravimetric
analysis (TGA) was performed using Q500 Thermogravimetric Analyzer
(TA Instruments, USA), and the samples were scanned from 35 to 800 °C
at a heating rate of 10 °C/min under N2 atmosphere. BET data were taken
on Tristar II 3020 (Micromeritics Instrument Corporation, USA) surface
1078 Y. Wang et al. / Materials Science and Engineering C 69 (2016) 1075–1080

Fig. 2. FTIR spectra of (a) SBA-15, (b) SBA-15-PSPH and (c) SBA-15-PSPH-Cl.

area analyzer with nitrogen adsorption-desorption isotherms on the sur-

face areas. Fig. 4. XRD and SXRD diffraction patterns of (a) SBA-15, (b) SBA-15-PSPH and (c) SBA-15-
PSPH-Cl.
3. Results and discussion

3.1. SEM and TEM oxidative chlorine [30]. The additional peaks appeared at 2978 cm−1
and 2935 cm−1 in Fig. 2b and c were ascribed to the symmetric and
Fig. 1 showed the electron microscopy images of SBA-15 and SBA- asymmetric stretching vibrations of C-CH3 and C-CH2 in PSPH, respec-
15-PSPH. TEM images in Fig. 1a and b showed that both the pristine tively. Therefore, the FT-IR spectra demonstrated that SBA-15 was suc-
sample and modified one have a uniform one dimensional straight po- cessfully modified with PSPH.
rous structure, which indicates that the mesoporous channels were
slightly affected by the modification with PSPH. And the morphology
of SBA-15 was not affected by the modification reaction. For SBA-15,
the SEM image showed well-defined long strip particles with size rang-
ing from hundreds to one thousand nanometer, and diameter ranging
from 0.5 to 1 μm (Fig. 1c and d).

3.2. FT-IR and XPS spectra

In order to remove the unreact PSPH on the surface of SBA-15, the

product was extracted with ethanol 24 h after the reaction. The FT-IR
spectra of SBA-15, PSPH-modified SBA-15 (SBA-15-PSPH), chlorinated
PSPH-modified SBA-15 (SBA-15-PSPH-Cl) were shown in Fig. 2. The
peak at 1072 cm−1 was a typical stretching vibration of Si-O-Si group
in SBA-15. Compared with SBA-15, SBA-15-PSPH presented a new
peak appeared at 1702 cm−1 in Fig. 2b, which corresponds to the
stretching vibrations of imide carbonyl bond in PSPH. This proved that
the PSPH has combined with SBA-15 by chemical bonds successfully
[29]. After chlorination, the vibrational band shifted from 1702 to
1716 cm− 1 as a result of the electron-withdrawing effect of the

Fig. 5. N2 adsorption-desorption isotherms and pore size distribution curves of (a) SBA-15,
Fig. 3. XPS spectra of (a) SBA-15, (b) SBA-15-PSPH and (c) SBA-15-PSPH-Cl. (b) SBA-15-PSPH.
 Y. Wang et al. / Materials Science and Engineering C 69 (2016) 1075–1080 1079

Table 1
Brunauer-Emmett-Teller result for SBA-15 and SBA-15-PSPH.
Sample Surface area (m2/g)a Pore volume (cm3/g)b Pore size (nm)c
SBA-15 724.81 0.97 5.59
SBA-15-PSPH 58.26 0.08 5.02
a of SBA-15-PSPH has sharply decreased after grafting with PSPH. The p/
Surface area was calculated by BET methods.
b
Pore volume was got from BJH Adsorption cumulative volume of pores between 1.70
and 300.00 nm.
c
Pore size was estimated using BJH Adsorption average pore width (4 V/A).
The successful modification of SBA-15 with PSPH was further con-
firmed by XPS. As shown in Fig. 3, there were new signals corresponding
to nitrogen (N 1s: 399.97 eV) and carbon (C 1s: 284.57 eV) on the sur-
face of SBA-15-PSPH, which proved that PSPH was successfully coated
on the surface of SBA-15. Compared with SBA-15 and SBA-15-PSPH,
the peak of chlorine (Cl 2p: 200.37 eV) appeared only on the surface
of SBA-15-PSPH-Cl, which demonstrated that oxidative chlorine was
successfully deposited on the surface of SBA-15. Based on the above re-
sults, we can conclude that PSPH was completely coated onto the sur-
face of SBA-15.
3.3. XRD
XRD and SXRD were used to analyze the crystalline structure and
pore organization of SBA-15, SBA-15-PSPH, and SBA-15-PSPH-Cl as
shown in Fig. 4. In the small-angle XRD diffraction patterns, all three
samples showed the typical peaks corresponding to the (100), (110)
and (200) lattice planes which belong to the two-dimensional ordered
hexagonal pore with p6mm space structure [31,32]. It means that the
modified with PSPH and chlorination have not affected the ordered
pore structure of SBA-15. The N2 adsorption-desorption isotherms of
BET analysis also correspond to the result of SXRD. Large-angle XRD dif-
fraction patterns (2θ = 10–70°) showed typically non-crystalline phase
structure, and did not show any significant changes after coating with
PSPH. The original and modified samples indicated that the non-crystal-
line phase of SBA-15 was not changed after the attachment of PSPH onto
the surface of SBA-15.
surface area, uniform pore size, and roundness slit. SBA-15 modified
with PSPH showed the same type of isotherms and hysteresis loops, in-
dicating that the mesoporous structure and roundness slit were
retained. Compared with that of SBA-15, the adsorbed volume of SBA-
15-PSPH was obviously reduced, which revealed that the surface area
po position in the N2 adsorption-desorption isotherms corresponds to
the diameter of the mesopore. Small pores appeared at low pressure,
and the large pores appeared at higher pressures. The pore size distribu-
tions of SBA-15 and SBA-15-PSPH were evaluated using BJH method. As
shown in Fig. 5, the pore size of SBA-15 was 7 to 10 nm and SBA-15-
PSPH was 5 to 7 nm. The BET data (Table 1) showed that the surface
area, pore volume, and pore size have changed enormously after modi-
fication, from 724.81 m2/g, 0.97 cm3/g, and 5.59 nm to 58.26 m2/g,
0.08 cm3/g, and 5.02 nm, respectively. It demonstrated that PSPH was
successfully grafted onto SBA-15, and the polymer had also changed
the pores on the surface of SBA-15 and the channels in some degree.
3.5. Thermal properties
The thermogravimetric analysis (TGA) of SBA-15, SBA-15-PSPH, and
SBA-15-PSPH-Cl was presented in Fig. 6. For SBA-15 (Fig. 6a), the weight
loss of 3% between 35 °C and 800 °C was caused by the evaporation of
physically and chemically adsorbed water, and the dehydroxylation of
silicon hydroxyl. As for the SBA-15-PSPH and SBA-15-PSPH-Cl
samples, there was an obvious mass-loss step in the temperature
range from 35 °C to 800 °C. The weight loss (about 25%) was mainly
due to the degradation of PSPH obtained from SBA-15. As for the SBA-
15-PSPH-Cl sample (Fig. 6c), the notable weight loss should be divided
into two parts. The first prominent weight loss of SBA-15-PSPH-Cl
starting at 200 °C was attributed to the decomposition of N\\Cl
chemical bonds, while the second weight loss in the range of 440 °C to
800 °C was corresponded to the degradation of PSPH. Therefore, it can
be concluded that PSPH has successfully loaded on SBA-15 (about
25 wt%).
3.6. Antibacterial efficacy

3.4. BET surface area analysis
Fig. 5a and b presented the nitrogen adsorption/desorption iso-
therms and pore sizes of SBA-15 and SBA-15-PSPH, respectively. The re-
sults of BET surface areas, pore volumes and pore sizes were presented
in Table 1. According to the standard classification of isotherms, Fig. 5a
showed the typical type IV isotherms, and exhibited type H1 hysteresis
loops at relative pressure range from 0.6 to 0.8. All of these were as-
cribed to mesoporous structure of the sample, which offers higher
SBA-15, SBA-15-PSPH, and SBA-15-PSPH-Cl were challenged with S.
aureus and E. coli O157:H7 at concentrations of 8.05 and 7.92 logs, re-
spectively, and the antibacterial efficacies were shown in Table 2. It
can be seen that SBA-15 and SBA-15-PSPH show certain degree of log
reductions with different contact times, which was mainly caused by
the adhesion of bacteria on the surface and pores of SBA-15 and SBA-
15-PSPH. The chlorinated modified sample with the chlorine loading
of 2.39% completely inactivated S. aureus and E. coli O157:H7 with log
reduction of 8.05 and 7.92 within 1 min, respectively.

Table 2
Antibacterial efficacies of SBA-15, SBA-15-PSPH and SBA-15-PSPH-Cl against bacteria.

S. aureusa E. coli O157:H7b

Sample Contact time (min) Log reduction Log reduction

SBA-15 1 1.10 0.74

5 1.14 0.96
10 1.17 0.99
30 1.44 1.09
SBA-15-PSPH 1 1.07 0.84
5 1.13 0.94
10 1.22 1.00
30 1.33 1.06
SBA-15-PSPH-Clc 1 8.05 7.92
5 8.05 7.92
10 8.05 7.92
30 8.05 7.92
a
The inoculum population was 8.05 logs.
b
The inoculum population was 7.92 logs.
c
Fig. 6. TGA analysis of (a) SBA-15, (b) SBA-15-PSPH and (c) SBA-15-PSPH-Cl. Cl+ loaded on samples was 2.39% ± 0.01 wt%.
1080 Y. Wang et al. / Materials Science and Engineering C 69 (2016) 1075–1080
4. Conclusions
The new kind of antibacterial porous material high surface area and
pore volume was successfully prepared. The chlorinated samples
showed outstanding antibacterial efficacies against S. aureus (8.05
logs) and E. coli O157:H7 (7.62 logs) within 1 min of contact time re-
spectively. The polymeric N-halamine precursor, PSPH, was successfully
synthesized and coated to the surface of mesoporous molecular sieves
with covalent bonds. Some pores of SBA-15 were blocked by PSPH.
However, the morphology and structure of the modified mesoporous
molecular sieves were slightly affected. The modified SBA-15 presented
good thermal and structure stability. Considering the high surface area,
pore volume and powerful antibacterial property, the N-halamine mod-
ified SBA-15 may have great potential for practical application in water
treatment or biomedical materials.
Acknowledgements
The authors thank the research funds from the Science and Technol-
ogy Department of Jiangsu Province of China (BY2014023-09,
BY2015019-23), the Project for Jiangsu Scientific and Technological In-
novation Team, and the Scientific Research Foundation for Returned
Overseas Chinese Scholars, Ministry of Education, China.
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