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.