Colloids and Surfaces B: Biointerfaces 122 (2014) 294–300
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Colloids and Surfaces B: Biointerfaces
jo ur nal ho me p ag e: www.elsevier.com/locate/colsurfb
Air-ozonolysis to generate contact active antimicrobial surfaces:
Activation of polyethylene and polystyrene followed by covalent graft
of quaternary ammonium salts
Tania Fadida
a,b
, Yulia Kroupitski
a,b
, Uri M. Peiper
c
, Tatyana Bendikov
d
,
Shlomo Sela (Saldinger)
a
, Elena Poverenov
a,∗
a
Department of Food Quality and Safety, The Volcani Center, ARO, PO Box 6, Bet Dagan 50250, Israel
b
Department of Biochemistry, The Hebrew University of Jerusalem, Rehovot 76100, Israel
c
Department of Agricultural Engineering, The Volcani Center, ARO, PO Box 6, Bet Dagan 50250, Israel
d
Department of Chemical Research Support, Weizmann Institute of Science, Rehovot 76100, Israel
a r t i c l e i n f o
Article history:
Received 11 May 2014
Received in revised form 25 June 2014
Accepted 2 July 2014
Available online 10 July 2014
Keywords:
Air-ozonolysis
Contact active surface
Quaternary ammonium salts
Antimicrobial surface
Polystyrene
Polyethylene
a b s t r a c t
Air-ozonolysis was revealed as an accessible and effective approach for surface activation and fur-
ther functionalization of hydrocarbon polymers. Antimicrobial contact active polyethylene (PE) and
polystyrene (PS) were designed by generation on their surfaces OH-functional groups and covalent graft
of dimethyloctadecyl [3-(trimethoxysilyl) propyl] ammonium chloride (C
18
-TSA) quaternary ammonium
salt. The shortened analog, trimethyl [3-(trimethoxysilyl) propyl] ammonium chloride (C
1
-TSA), was also
covalently attached to the activated PE and PS surfaces. X-ray photoelectron spectroscopy (XPS) and FTIR
confirmed the surface modifications. Scanning electron (SEM) and confocal microscopy were utilized to
monitor surface morphology and bacteria interactions. The antimicrobial effect of the C
18
-TSA grafted
polymer surfaces was demonstrated on Gram-negative and Gram-positive bacteria species including
human pathogen, Salmonella enterica. The shorter C
1
-TSA grafted polymers did not demonstrate bacteri-
cidal activity, suggesting the critical role of the alkyl chain length. The described strategy may establish
a new general and safe platform for future development and application of contact active antimicrobial
polymers.
© 2014 Elsevier B.V. All rights reserved.
1. Introduction
Material surfaces are most prone to bacterial colonization that
causes adverse effects in various areas, resulting in contamina-
tion of medical devices, food contamination and biofouling [1].
To reduce bacterial adhesion and proliferation, contact active
antimicrobial approaches were developed [2,3]. Contact active
approach involves a durable (usually covalent) linkage of an
antimicrobial moiety to a material’s surface. Being surface linked,
the antimicrobial agent is not consumed or released, providing
important advantages in terms of human and environmen-
tal safety [4]. In addition, such active surfaces can be reused
multiple times. Due to these environmental and operational
advantages, contact active antimicrobial materials (CAAM), are of
high research and applicative interest [4,5]. Contact active surface
∗
Corresponding author. Tel.: +972 3 9683354; fax: +972 3 968 3692.
E-mail address: elenap@volcani.agri.gov.il (E. Poverenov).
modifications were achieved through the chemical grafting
of antimicrobial polymers, such as N-alkylated poly(4-
vinylpyridine) [3], poly(4-vinyl-N-methylpyridinium iodide)
[6], poly(butylmethacrylate)-co-poly(Boc-aminoethyl methacry-
late) [7], covalent linkage of quaternary derivatives of acrylic
acid [8] and grafting of many others antimicrobial moieties [9].
An additional domain in contact active research involves surface
linkage of antimicrobial peptides [9–12].
Polyethylene (PE) and polystyrene (PS) are among the most
prevalent polymers that are used in all areas of modern life, ranging
from various packaging material to medicinal equipment. PE and
PS have no inherent heteroatom functional groups, and therefore
surface activation is required for binding of an antimicrobial moiety
to these polymers. Chemical activation methods that utilize strong
oxidative agents such as chromic, nitric or sulfuric acids, potassium
permanganate and hydrogen peroxide can generate functional
groups on the polymer surface [13]. However, such treatments
produce hazardous chemical waste and may cause undesirable
changes of the bulk polymer properties. Physical approaches such
http://dx.doi.org/10.1016/j.colsurfb.2014.07.003
0927-7765/© 2014 Elsevier B.V. All rights reserved.