Carbohydrate Polymers 103 (2014) 456–465
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Carbohydrate Polymers
jo u r n al homep age: www.elsevier.com/locate/carbpol
Preparation and characterization of bio-nanocomposite films of agar
and silver nanoparticles: Laser ablation method
Jong-Whan Rhim
a,∗
, Long-Feng Wang
a
, Yonghoon Lee
b
, Seok-In Hong
c
a
Department of Food Engineering and Bionanocomposite Research Institute, Mokpo National University, 61 Dorimri, Chungkyemyon, Muangun,
534-729 Jeonnam, Republic of Korea
b
Department of Chemistry, Mokpo National University, 61 Dorimri, Chungkyemyon, Muangun, 534-729 Jeonnam, Republic of Korea
c
Korea Food Research Institute, 516 Baekhyun-dong, Bundang-gu, Seongnam-si, 463-746 Gyonggi-do, Republic of Korea
a r t i c l e i n f o
Article history:
Received 4 October 2013
Received in revised form
23 December 2013
Accepted 26 December 2013
Available online 5 January 2014
Keywords:
Laser ablation
Silver nanoparticles
Agar
Bio-nanocomposites
Antimicrobial activity
a b s t r a c t
Silver nanoparticles (AgNPs) were prepared by a laser ablation method and composite films with the
AgNPs and agar were prepared by solvent casting method. UV–vis absorbance test and transmission elec-
tron microscopy (TEM) analysis results revealed that non-agglomerated spherical AgNPs were formed by
the laser ablation method. The surface color of the resulting agar/AgNPs films exhibited the characteris-
tic plasmonic effect of the AgNPs with the maximum absorption peaks of 400–407 nm. X-ray diffraction
(XRD) test results also exhibited characteristic AgNPs crystals with diffraction peaks observed at 2 val-
ues of 38.39
◦
, 44.49
◦
, and 64.45
◦
, which were corresponding to (1 1 1), (2 0 0), and (2 2 0) crystallographic
planes of face-centered cubic (fcc) silver crystals, respectively. Thermogravimetric analysis (TGA) results
showed that thermal stability of the agar/AgNPs composite films was increased by the inclusion of metal-
lic silver. Water vapor barrier properties and surface hydrophobicity of the agar/AgNPs films increased
slightly with the increase in AgNPs content but they were not statistically significant (p > 0.05), while
mechanical strength and stiffness of the composite films decreased slightly (p < 0.05). The agar/AgNPs
films exhibited distinctive antimicrobial activity against both Gram-positive (Listeria monocytogenes)
and Gram-negative (Escherichia coli O157:H7) bacterial pathogens.
© 2014 Elsevier Ltd. All rights reserved.
1. Introduction
Silver has long been recognized as an effective antimicrobial
agent with a broad spectrum of antimicrobial activity against not
only both Gram-positive and Gram-negative pathogenic bacte-
ria but also viruses and other eukaryotic microorganisms (Russell
& Hugo, 1994). Accordingly, with the advent of nanotechnol-
ogy, silver nanoparticles (AgNPs) have been emerged in the
development of an antibacterial, antifungal, antiviral, and anti-
inflammatory agent (Rai, Yadav, & Gade, 2009; Vaidyanathan,
Kalishwaralal, Gopalram, & Gurunathan, 2009). Especially, in food
packaging sectors, AgNPs have been exploited for the preparation
of antimicrobial active food packaging films due to their strong
antimicrobial activity with high thermal stability (Llorens, Lloret,
Picouet, Trbojevich, & Fernandez, 2012).
The antimicrobial efficiency of AgNPs-included antimicrobial
packaging films is greatly influenced by various factors such as
particle size, and its distribution, degree of particle agglomera-
tion, silver content, and interaction of silver surface with the base
∗
Corresponding author. Tel.: +82 61 450 2423; fax: +82 61 454 1521.
E-mail addresses: jwrhim@mokpo.ac.kr, jwrhim@hanmail.net (J.-W. Rhim).
polymer (Kim et al., 2007). Above all, AgNPs should be well dis-
persed through polymer matrix without agglomeration. Therefore,
it is essential to obtain AgNPs with proper dimensions and to choose
proper polymeric materials for the preparation of efficient antimi-
crobial packaging films with AgNPs.
Conventionally, AgNPs have been produced by the reduction
of silver nitrate (AgNO
3
) using chemical reducing agents such as
sodium borohydride, dimethyl formamide, triethanolamine, and
hydrazine (Yoksan & Chirachanchai, 2010). However, such chem-
ical reduction method is not recommended since the chemicals
are highly reactive and known to pose a potential environ-
mental hazard and biological risks. Instead, a variety of green
technologies for the preparation of AgNPs have been developed
(Habbalalu, Lalley, Nadagouda, & Varma, 2013). For example, bio-
logical materials such as plant extracts, bacteria, fungi, and yeast
have been used as mediators for the synthesis of AgNPs (Rhim,
Wang, & Hong, 2013). Recently, another type of green technol-
ogy has been tested using various carbohydrates such as glucose,
sucrose, starch, chitosan, and marine polysaccharides. In these
technologies, the biopolymers act as both reducing and stabiliz-
ing agents and also as polymer matrix for carrying AgNPs (Rhim
et al., 2013; Venkatpurwar & Pokharkar, 2011). Furthermore, these
approaches using biopolymers are safe, biocompatible, nontoxic
0144-8617/$ – see front matter © 2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.carbpol.2013.12.075