Thesis (PhD)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: The main objective of this study was to develop electrospun nanofibres with both antimicrobial and antibiofouling properties for possible application in water filtration. To do this, two routes were investigated: firstly, the use of biocides and bactericidal copper salts to introduce bactericidal properties on electrospun nanofibres. Secondly, the modification of polymers using furanone compounds to obtain nanofibres with the ability to repel microbial attachment. Fabrication of biocide-containing PVA nanofibres was successful. This was achieved through direct doping of PVA solutions with AquaQure which is an aqueous biocide comprising of mainly Cu2+ and Zn2+, prior to the electrospinning process coupled with chemical crosslinking using glyoxal. The conventional needle based electrospinning technique was used to fabricate these nanofibrous mats. The presence of the constituents of AquaQure on surfaces of PVA/AquaQure nanofibrous mats was confirmed using energy dispersive x-ray analysis (EDX). ATR/FTIR, XRD, TGA, DSC and SEM techniques were used to do chemical and thermal analysis of the nanofibres in comparison with pristine PVA nanofibres. These nanofibres demonstrated antimicrobial activity of up to 5 log against the Gram-positive strain S. aureus Xen 36 and Gram-negative strains E. coli Xen 14, S. typhimurium Xen 26, P. aeruginosa Xen 5 and K. pneumoniae Xen 39. Because of crosslinking, these fibres also demonstrated good water stability. Leaching of the ions constituting AquaQure was limited and compared with South African national standards for drinking water, the water filtered through these nanofibress was deemed safe for human consumption. Bioluminescence imaging and fluorescence microscopy were used to confirm antimicrobial activity results obtained from plate counting. These nanofibres demonstrated satisfactory antimicrobial efficiency but did not repel microbial attachment. The second part of this study entailed the investigation of copper-doped PVA and SMA nanofibres for antimicrobial activity. Although bactericidal properties of copper are well documented, its selection was based on the fact that it is the main constituent of the AquaQure. Bubble electrospinning was used instead of needle electrospinning to upscale nanofibre production. Similar techniques as those used in PVA/AquaQure nanofibres were used to characterize the copper functionalized nanofibres. Even though these nanofibres demonstrated exceptional antimicrobial efficacy (up to 5 log) for all the strains, bioluminescence imaging indicated a trend for these cells to enter a dormant state on contact with the copper containing-nanofibres. The last part of this project involved testing of free furanone compounds as well as surface-tethered furanone-modified nanofibres for their antibiofouling potentials. To do this, blends of 2,5-dimethyl-4-hydroxy-3(2H)furanone (DMHF) (5% wt/vol) with PVA (10% wt/vol) were prepared and electrospun to produce PVA/DMHF nanofibres. The free furanones and furanone-modified nanofibres demonstrated not only antibiofouling properties but also antimicrobial activity. Other furanone compounds with 3(2H) and 2(5H) cores were synthesized. The synthesis of these furanone compounds (5-(2-(2-aminoethoxy)ethoxy)methyl)-2(5H)furanone and 4-(2-(2-aminoethoxy)-2,5-dimethyl-3(2H)-furanone) was successful. Their structures and molar masses were confirmed using 1H NMR and ES mass spectroscopy. These furanones were then covalently immobilized on the SMA backbone. To test their antimicrobial and antibiofouling activity, the furanone-modified polymer was dissolved in an ethanol and methanol mixture (1:1) and electrospun to produce nanofibres. The free furanone and furanone-modified SMA nanofibres derived from 4-(2-(2-aminoethoxy)-2,5-dimethyl-3(2H)-furanone demonstrated high antibiofouling and antimicrobial efficiency against the Gram-positive strain S. aureus Xen 36 and Gram-negative strains E. coli Xen 14, S. typhimurium Xen 26, P. aeruginosa Xen 5 and K. pneumoniae Xen 39. The 2(5H) furanone on the other hand had limited activity against the strains. These nanofibres were also characterized and compared with their pristine polymer counterparts and leaching experiments were conducted using GC-MS. / AFRIKAANSE OPSOMMING: Die hoofdoel van hierdie studie was om nanovesel filtrasie nanofibre met beide antimikrobiese en aanpakwerende eienskappe te ontwikkel. Twee verskillende metodes is ondersoek. Eerstens is biosiede en bakteriee-dodende koper soute gebruik om antimikrobiese nanovesels te lewer. Tweedens is nanovesels met furanoon samestellings gemodifiseer om nanovesels te lewer wat mikrobiese aanhegting voorkom. Die fabrisering van biosied-bevattende PVA nanovesel nanofibre was suksesvol. AquaQure, ‟n biosied wat hoofsaaklik uit Cu2+ en Zn2+ bestaan, is direk by PVA oplossings gevoeg voor die elektrospin proses, en is gevolg deur chemiese kruisbinding deur middel van “glyoxal”. Die nanovesels is neergele in ‟n ongeweefde mat deur middel van die konvensionele naald-gebasseerde elektrospin proses. Verspreidings X-staal analises (EDX) is gebruik om die teenwoordigheid van AquaQure komponente in en op die oppervlakte van die PVA/aquaqure nanovesel matte te bevestig. ATR/FTIR, UV-Vis, XRD, TGA, DSC en SEM tegnieke is gebruik vir chemiese en termiese analises om sodoende PVA/aquacure nanovesels met ongemodifiseerde PVA nanovesels te vergelyk. PVA/aquacure nanovesels het ‟n antimikrobiese aktiwiteit van tot 5 log reduksie getoon teen Gram-positiewe S. aureus Xen 36 en Gram-negatiewe E. coli Xen 14, S. typhimurium Xen 26, P. aeruginosa Xen 5 en K. pneumoniae Xen 39. Die vesels was stabiel in water na kruisbinding. Slegs beperkte uitloging van Aquaqure Cu2+ en Zn2+ ione is waargeneem, en water wat deur die PVA/aquacure nanovesels gefiltreer is, is volgens Suid Afrikaanse Nasionale Standaarde vir drinkwater steeds veilig vir menslike gebruik. Behalwe vir die plaat-tellingsmetode het bio-lumiserende fotos en fluoroserende mikroskopie ook die antimikrobiese aktiwiteit van die vesels bevestig. Die vesels het bevredigende antimikrobiese efektiwiteit getoon, maar kon nie mikrobiese aanhegting voorkom nie. In die tweede gedeelte van die werk is die antimikrobiese aktiwiteit van PVA en SMA vesels wat met koper verreik is, ondersoek. Alhoewel die bakteriee dodende eienskappe van koper reeds goed gedokumenteer is, is hierdie ondersoek gedoen op grond van die feit dat koper een van die hoof komponente van aquaqure is. Nanovesels is uit koper-verreikte oplossings van PVA en SMA deur middel van die borrel-gebasseerde elektrospin tegniek gefabriseer, ten einde die opbrengs van nanovesels te verhoog. Fisiese kruisbinding deur middel van hitte behandeling is toegepas ten einde die stabiliteit van die vesels in water te verbeter. Dieselfde karakteriseringstegnieke wat gebruik is vir die PVA/aquacure vesels is op hierdie vesels toegepas. Alhoewel die vesels uitstekende antimikrobiese aktiwiteit van tot 5 log reduksie gedemonstreer het, het bio-lumiserende beeldvorming getoon dat die selle ‟n dormante stadium binnegaan na kontak met hierdie vesels. In die laaste gedeelte van die projek is vrye furanoon samestellings en nanofibre met oppervlak-gehegde furanone getoets vir aanpakwerende potensiaal. Om dit te bewerkstellig was „n mengsel van 2,5 – dimethyl-4-hydroxy-3(2H) furanone (DMHF) (5% wt/vol) en PVA (10% wt/vol) voorberei en gebruik om PVA/DMHF nanovesel filtrasie nanofibre te produseer deur middel van die elektrospin proses. Die vrye furanone en furanoon-gemodifiseerde nanofibre het nie alleen aanpak weerstandbiedende einskappe gedemonstreer nie maar ook antimikrobiese eienskappe. DMHF was gebruik as die begin material om furanoon samestellings te produseer met 3(2H) en 2(5H) kerne. Die sintesis van hierdie furanone se samestellings (5-(2-(2-aminoethoxy)ethoxy)methyl)-2(5H)furanone en 4-(2-(2-aminoethoxy)-2,5-dimethyl-3(2H)-furanone) was suksesvol. Hulle strukture en molere massas was bevestig met 1H NMR en ES massa spektrometrie. Hierdie furanone is daarna kovalent ge-immobiliseer op die SMA rugbeen. Om hulle antimikrobiese en aanpakwerende aktiwitiet te toets, is die furanoon-gemodifiseerde polimeer opgelos in „n etanol en metanol mengsel (1:1) en ge-elektrospin om nanovesel filtrasie nanofibre te produseer. Die furanone en furanoon-gemodifiseerde nanovesel filtrasie nanofibre afkomstig van 4-(2-(2-aminoethoxy)-2,5-dimethyl-3(2H)-furanone het hoe aanpakwerende en antimibrobiese effektiewitiet getoon teenoor die Gram-positiewe S. aureus Xen 36 en Gram-negatiewe E. coli Xen 14, S. typhimurium Xen 26, P. aeruginosa Xen 5 and K. pneumoniae Xen 39. Hierdie nanovesel filstrasie nanofibre is ook gekarakteriseer en vergelyk met die ongemodifiseerde polimeer. „n Uitlogings eksperiment is uitgevoer deur gebruik te maak van GC-MS.

Die Synthese von oberflächengepfropften Polypeptoidbürsten durch die Oberflächeninitiierte Ringoffnungspolmerisation von N-substituierten N-carboxyanhydriden wird beschrieben. Die entstehenden Schichten werden durch Zelladhäsionsexperimente und Oberflächenplasmonenresonanzspektroskopie auf ihre Antibiofouling-Eigenschaften untersucht. UV-Lithographie und Mikrokontaktdrucken wird zur Herstellung von strukturierten Oberflächen verwendet. Eine Funktionalisierung der Strukturen wird mit Fluoreszenzmikroskopie und Fluoreszenzmapping nachgewiesen. Ein zweiter Schwerpunkt befasst sich mit der Synthese von Kompositschichten. Oberflächengepropfte polykationische Polymerbürsten dienen als Einlagerungsmedium für negativ geladene Nanopartikel. Durch calcinieren werden poröse Schichten erhalten. Die Anwendung des Verfahrens auf ein Partikelsystem generiert poröse Core-Shell-Partikel.

Die Synthese von oberflächengepfropften Polypeptoidbürsten durch die Oberflächeninitiierte Ringoffnungspolmerisation von N-substituierten N-carboxyanhydriden wird beschrieben. Die entstehenden Schichten werden durch Zelladhäsionsexperimente und Oberflächenplasmonenresonanzspektroskopie auf ihre Antibiofouling-Eigenschaften untersucht. UV-Lithographie und Mikrokontaktdrucken wird zur Herstellung von strukturierten Oberflächen verwendet. Eine Funktionalisierung der Strukturen wird mit Fluoreszenzmikroskopie und Fluoreszenzmapping nachgewiesen. Ein zweiter Schwerpunkt befasst sich mit der Synthese von Kompositschichten. Oberflächengepropfte polykationische Polymerbürsten dienen als Einlagerungsmedium für negativ geladene Nanopartikel. Durch calcinieren werden poröse Schichten erhalten. Die Anwendung des Verfahrens auf ein Partikelsystem generiert poröse Core-Shell-Partikel.

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The steep rise in the contamination of natural water sources, has led to an increasing demand for alternate solutions to cater safe drinking water to mankind. Water treatment by separation technology utilizes semipermeable membranes to filter the contaminants commonly present in potable water. In this context, the current work focuses on the development of membranes that are affordable, exhibit chemical resistance and can be developed at industrial scale. By blending two immiscible polymers like polyethylene (PE) and polyethylene oxide (PEO), different morphologies can be generated and porous structures can be developed by selectively etching the water soluble phase (PEO). Microorganisms in the feed stream often tend to foul the membrane by forming biofilms on the surface that tends to increase the resistance offered by the membrane. Therefore, preventing this biofilm is a key challenge in this field and can be overcome by use of functional group or materials that prevent the attachment or growth of microorganisms on the surface, while maintaining a good permeation rate of water. This thesis entitled “Porous Antibacterial Membranes Derived from Polyethylene (PE)/Polyethylene oxide (PEO) Blends and Engineered Nanoparticles” systematically studies the various morphologies generated by melt blending polyethylene (PE)/polyethylene oxide (PEO) in presence and absence of a compatibilizer (maleated PE). Porous structures are developed by selectively etching PEO from the blends and the nature of the pores, which is dependent on the blend composition, is assessed by tomography. The potential of these membranes are discussed for water purification application. Further, various modifications either on the surface or in the bulk have been systematically studied. For instance, incorporation of biocidal agents like graphene oxide (GO) and modified GO in the matrix and coating/grafting of membrane surface with biocidal agents like silver (Ag), GO for preventing the biofouling and to meet the specific requirements for safe drinking water. The thesis consists of ten chapters. Chapter 1 is a review on polymer blends for membrane applications. This chapter covers the fundamentals of polymer blends in transport processes and compares the merits and demerits of the conventional methods. This chapter mainly covers the melting blending technique and the optimizing parameters for obtaining a desired morphology. Further, the various methodologies for stabilization of the morphology against post processing operation have been discussed. The various methodologies for designing membranes (for water purification) that suppress or inhibit the bacterial activity on the membrane surfaces have been discussed elaborately. Chapter 2 outlines the materials, experimental set-up and procedures employed. Chapter 3 focuses on the morphologies that are developed during the blending of PE/PEO with varying weight ratios. The morphologies developed are supported by SEM analysis. The factors governing the localization of particles in PE/PEO blends are discussed in detail. The gradient in morphology obtained during post processing operations is highlighted. Based on the type of morphologies obtained, the thesis is divided into two parts as (I) membranes designed using matrix droplet type of morphology and (II) membranes designed using co-continuous morphology. Part I consists of four chapters that involves the development of membranes utilizing matrix droplet morphology. Chapter 4 focuses on the development of morphology, the length scales of which are smaller than a bacterial cell. This ensures sieving of the contaminants that are commonly present in the drinking water though the surface of the membranes may not be antibiofouling. Thus a passive strategy of antibiofouling has been employed by blending biocidal agents like GO and amine modified GO during melt mixing. The antibacterial mechanism and its effect on bacterial activity have been thoroughly studied. Chapter 5 focuses on modification of membrane by incorporating silver decorated GO in the bulk. The effect of incorporation of these particles and their effect on bacterial activity have been discussed systematically. Chapter 6 emphasizes on the surface coating of membrane with chitosan to enhance the antibacterial activity and antibiofouling. Chapter 7 focuses on the development of membrane with pore sizes that are larger than a bacterial cell. These membranes are grafted with antibacterial polymers like polyethylene imine (PEI) and Ag to achieve antibacterial and antibiofouling surface. The possible mechanism of bacterial inactivity is described and the leaching of Ag from the membranes has been discussed. Part II of the thesis focuses on the development of co-continuous morphology in PE/PEO blends and has been assessed using 3D tomography. Chapter 8 describes the development of co-continuous morphology in PE/PEO blend. 2D and 3D micrographs have been corroborated for understanding the morphology evolution during post processing operation like remelting or hot-pressing. The blend has been strategically compatibilized to arrest the morphology and retain the co-continuity in the blends. GO was anchored onto the surface of the membrane by rendering suitable surface active groups. The antibiofouling and bacterial inhibition was studied in detail. The effect of anchoring GO on the membrane surface has been discussed with respect to their membrane performance and its antibacterial activity. Chapter 9 discusses the development of membranes using PE based Ionomer (Surlyn) and PEO. The Ionomer provided active sites for reducing silver nitrate directly onto the surface of PE to render antibacterial surface which otherwise requires a two-step protocol in the case of inert PE. The effect of coating Ag on the membrane performance and its antibacterial activity is elaborated. Chapter 10 sums up the major conclusions from each chapter and highlights the outcome of the work.