Mesoporous Iron Oxide Synthesized Using Poly(styrene‑b‑acrylic
acid‑b‑ethylene glycol) Block Copolymer Micelles as Templates for
Colorimetric and Electrochemical Detection of Glucose
Shunsuke Tanaka,
†,‡,+
Yusuf Valentino Kaneti,*
,‡,+
Ripon Bhattacharjee,
§,∥
Md Nazmul Islam,
§,∥
Rina Nakahata,
⊥
Nawfel Abdullah,
†
Shin-ichi Yusa,
⊥
Nam-Trung Nguyen,
§,∥
Muhammad J. A. Shiddiky,*
,§,∥
Yusuke Yamauchi,*
,†,#,@
and Md. Shahriar A. Hossain*
,†,‡
†
Australian Institute of Innovative Materials (AIIM), University of Wollongong, North Wollongong, New South Wales 2500,
Australia
‡
International Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), 1-1 Namiki,
Tsukuba, Ibaraki 305-0044, Japan
§
School of Natural Sciences, Griffith University, Brisbane, Queensland 4111, Australia
∥
Queensland Micro- and Nanotechnology Centre, Griffith University, Brisbane, Queensland 4111, Australia
⊥
Department of Materials Science and Chemistry, University of Hyogo, 2167 Shosha, Himeji 671-2280, Japan
#
School of Chemical Engineering, The University of Queensland, Brisbane QLD 4072, Australia
@
Australian Institute for Bioengineering and Nanotechnology (AIBN), The University of Queensland, Brisbane QLD 4072, Australia
* S Supporting Information
ABSTRACT: Herein, we report the soft-templated preparation of
mesoporous iron oxide using an asymmetric poly(styrene-b-acrylic acid-b-
ethylene glycol) (PS-b-PAA-b-PEG) triblock copolymer. This polymer
forms a micelle consisting of a PS core, a PAA shell, and a PEG corona in
aqueous solutions, which can serve as a soft template. The mesoporous iron
oxide obtained at an optimized calcination temperature of 400 °C exhibited
an average pore diameter of 39 nm, with large specific surface area and pore
volume of 86.9 m
2
g
−1
and 0.218 cm
3
g
−1
, respectively. The as-prepared
mesoporous iron oxide materials showed intrinsic peroxidase-like activities
toward the catalytic oxidation of 3,3′,5,5′-tertamethylbenzidine (TMB) in
the presence of hydrogen peroxide (H
2
O
2
). This mimetic feature was
further exploited to develop a simple colorimetric (naked-eye) and
electrochemical assay for the detection of glucose. Both our colorimetric
(naked-eye and UV−vis) and electrochemical assays estimated the glucose
concentration to be in the linear range from 1.0 μM to 100 μM with a detection limit of 1.0 μM. We envisage that our integrated
detection platform for H
2
O
2
and glucose will find a wide range of applications in developing various biosensors in the field of
personalized medicine, food-safety detection, environmental-pollution control, and agro-biotechnology.
KEYWORDS: mesoporous metal oxides, iron oxide, block copolymers, soft-template, glucose detection
■
INTRODUCTION
Transition metal oxides are important classes of materials with
broad potential applications in catalysis,
1,2
sensors,
3−5
energy
storage and conversion,
6−9
and biomedical fields.
10−12
Among
various metal oxides, iron(III) oxide has been considered as one
of the most promising materials for electrochemical sensing due
to their abundance, low cost, high chemical and thermal
stabilities, as well as low toxicity and environmental friend-
liness.
13
The functional performance of iron oxide materials can
be greatly enhanced when their crystal sizes are confined to the
nanoscale and their morphologies are appropriately controlled
to yield a high surface area.
14
As such, many efforts have been
carried out to fabricate diverse morphologies of iron oxide
nanostructures, including nanorods,
15
nanotubes,
16
hollow
spheres,
17
and flower-like nanosheets.
18
In recent years, the synthesis of mesoporous materials have
attracted extensive research interests owing to their unique
morphology, large surface area, and pore volume, narrow pore
size distribution, controllable wall composition, and modifiable
surface properties.
19,20
Mesoporous metal oxide materials,
including mesoporous iron oxides have been fabricated mostly
through two main approaches: hard and soft-templating
Received: September 12, 2017
Accepted: November 29, 2017
Published: November 29, 2017
Research Article
www.acsami.org
Cite This: ACS Appl. Mater. Interfaces 2018, 10, 1039-1049
© 2017 American Chemical Society 1039 DOI: 10.1021/acsami.7b13835
ACS Appl. Mater. Interfaces 2018, 10, 1039−1049