Modified polymer surfaces with antimicrobial properties
File(s)
Author(s)
Alemi, Fatemeh
Type
Thesis or dissertation
Abstract
Biofilms are a multispecies community of bacterial cells that can establish over
time on biotic and abiotic surfaces. Biofilm growth and maturation on industrial
polymer surfaces poses a serious challenge to public health, industrial manufacturing,
oil and gas industries, food production and healthcare. As a result, there has been
increasing interest in the development of easily synthesised low-cost antimicrobial
polymer surfaces and coatings to inhibit, and/or perturb bacterial attachment and
biofilm viability.
This thesis was focused on modifying the surface of low cost commercial polymers, with
high-density polyethylene (HDPE) being used as the model substrate. Surface
modifications were performed using a range of approaches. These included different
surface oxidative treatment methods in order to evaluate their intrinsic antimicrobial
performance, and as an approach for improving the adhesion for other antimicrobial
coatings being investigated. Tin-dioxide thin-films and low/medium molecular weight
chitosan-zinc oxide nanocomposite coatings were also investigated and examined as
possible antimicrobial surface coating technologies for polymer materials, primarily for
HDPE. A key aim of this work was to evaluate microbial adhesion and biofilm viability at
the initial stages of biofilm maturation (early-stage biofilm), with successful
antimicrobial approaches then being further evaluated against a more mature biofilm
system.
This study confirms that the sulfuric-chromic acid surface oxidisation of HDPE and
polypropylene surfaces showed marked reductions in bacterial adhesion and viability,
with a decrease in attachment seen for both Gram-negative and positive bacterial
species with increasing surface oxidisation treatment time periods from 0 to 60
minutes. In particular, extended sulfuric-chromic acid oxidisation treatment times of 30
and 60 minutes significantly compromised microbial viability, such that there was no
agar growth of early-stage biofilm of Gram-negative organisms recovered from these
surfaces when cultured, even after 3 months of aging this polymer material under
standard laboratory conditions. The mechanism for this activity was ascribed to the
formation of chromium esters which are known reactive intermediates in the sulfuric-chromic acid oxidisation of HDPE, and their surface presence was further confirmed
using TOF-SIMS. Tin-dioxide nanoparticle coatings showed a reduction in the earlystage biofilm formation of Pseudomonas aeruginosa, irrespective of nanoparticle size
of the tin-dioxide coating used, which was also observed when coatings were deployed
on polypropylene and polycarbonate materials. A range of chitosan-zinc oxide
composite thin-films were examined which exhibited minimal viability reduction against
Escherichia coli early-stage biofilms. Therefore, this study could not affirm a significant
antimicrobial performance for the chitosan-ZnO nanocomposite coatings on oxidised
HDPE materials which was attributed to the loss of a key antimicrobial active functional
group in chitosan, the primary amines. However, optimisation of the chitosan-ZnO
formulations revealed some key trends, where increased concentrations of low
molecular weight chitosan in the presence of zinc-oxide in 1% acetic acid, resulted in a
2.8-log reduction of Escherichia coli due to the presence of primary amine substituents,
confirmed by a ninhydrin assay. Experiments performed against mature biofilms
prepared in a 24-hour aqueous environment found no antimicrobial performance on all
substrates and coatings tested.
time on biotic and abiotic surfaces. Biofilm growth and maturation on industrial
polymer surfaces poses a serious challenge to public health, industrial manufacturing,
oil and gas industries, food production and healthcare. As a result, there has been
increasing interest in the development of easily synthesised low-cost antimicrobial
polymer surfaces and coatings to inhibit, and/or perturb bacterial attachment and
biofilm viability.
This thesis was focused on modifying the surface of low cost commercial polymers, with
high-density polyethylene (HDPE) being used as the model substrate. Surface
modifications were performed using a range of approaches. These included different
surface oxidative treatment methods in order to evaluate their intrinsic antimicrobial
performance, and as an approach for improving the adhesion for other antimicrobial
coatings being investigated. Tin-dioxide thin-films and low/medium molecular weight
chitosan-zinc oxide nanocomposite coatings were also investigated and examined as
possible antimicrobial surface coating technologies for polymer materials, primarily for
HDPE. A key aim of this work was to evaluate microbial adhesion and biofilm viability at
the initial stages of biofilm maturation (early-stage biofilm), with successful
antimicrobial approaches then being further evaluated against a more mature biofilm
system.
This study confirms that the sulfuric-chromic acid surface oxidisation of HDPE and
polypropylene surfaces showed marked reductions in bacterial adhesion and viability,
with a decrease in attachment seen for both Gram-negative and positive bacterial
species with increasing surface oxidisation treatment time periods from 0 to 60
minutes. In particular, extended sulfuric-chromic acid oxidisation treatment times of 30
and 60 minutes significantly compromised microbial viability, such that there was no
agar growth of early-stage biofilm of Gram-negative organisms recovered from these
surfaces when cultured, even after 3 months of aging this polymer material under
standard laboratory conditions. The mechanism for this activity was ascribed to the
formation of chromium esters which are known reactive intermediates in the sulfuric-chromic acid oxidisation of HDPE, and their surface presence was further confirmed
using TOF-SIMS. Tin-dioxide nanoparticle coatings showed a reduction in the earlystage biofilm formation of Pseudomonas aeruginosa, irrespective of nanoparticle size
of the tin-dioxide coating used, which was also observed when coatings were deployed
on polypropylene and polycarbonate materials. A range of chitosan-zinc oxide
composite thin-films were examined which exhibited minimal viability reduction against
Escherichia coli early-stage biofilms. Therefore, this study could not affirm a significant
antimicrobial performance for the chitosan-ZnO nanocomposite coatings on oxidised
HDPE materials which was attributed to the loss of a key antimicrobial active functional
group in chitosan, the primary amines. However, optimisation of the chitosan-ZnO
formulations revealed some key trends, where increased concentrations of low
molecular weight chitosan in the presence of zinc-oxide in 1% acetic acid, resulted in a
2.8-log reduction of Escherichia coli due to the presence of primary amine substituents,
confirmed by a ninhydrin assay. Experiments performed against mature biofilms
prepared in a 24-hour aqueous environment found no antimicrobial performance on all
substrates and coatings tested.
Version
Open Access
Date Issued
2022-04
Date Awarded
2022-11
Copyright Statement
Creative Commons Attribution NonCommercial Licence
Advisor
Williams, Daryl
Sponsor
Engineering and Physical Sciences Research Council (EPSRC)
P&G
Publisher Department
Chemical Engineering
Publisher Institution
Imperial College London
Qualification Level
Doctoral
Qualification Name
Doctor of Philosophy (PhD)