Adverse interaction and subsequent adsorption of biomolecular species (i.e. fouling) pose a great hindrance for medical and clinical applications (e.g. biosensors). Research into the mechanism behind antifouling coatings have shown a strong link between surface hydration and antifouling behaviour due to the existence of a ‘water barrier’ which prevents proteins from adsorbing onto the surface. In a previous study, a short, mono(ethylene-glycol) silane adlayer (MEG-OH) showed significantly different antifouling behaviour in comparison to its homolog – lacking the internal ether oxygen (OTS-OH). In the present work, neutron reflectometry (and modeling) was used to investigate the water density profiles at MEG-OH and OTS-OH silane adlayers on quartz and Si/SiO2 to determine whether the internal ether oxygen affects the adlayers’ interaction with water. Despite the limitations of studying such ultrathin organic films, the two systems showed different hydration profiles supporting the link between surface hydration and antifouling.

Anaerobic membrane bioreactor (AnMBR) serves as a more sustainable form of wastewater treatment. However, biofouling is particularly detrimental to the performanceof AnMBRs. This dissertation focuses on understanding more about the biofouling in nMBR, and to devise strategies to control or make use of these biofoulant layers. First, we aim to investigate the microbial community structure of sludge and biofilm from 13 different AnMBRs. Our findings indicate 20 sludge core genera and 12 biofilm core genera (occurrence ≥ 90% samples) could potentially account for the AnMBR performance. Sloan neutral model analysis indicates the anaerobic microbial consortium between sludge and biofilm is largely affected by stochastic dispersal and migration processes (i.e., neutral assembly), suggesting that the majority of these core genera are not selectively enriched for biofilm formation. Therefore, the second part of this dissertation aims to minimize the growth of the overall bacterial cells attached on the membranes. For this, membranes embedded with zinc oxide (ZnO) and copper oxide (CuO) nanoparticles were examined for their antifouling efficacies. Our findings indicate both CuO and ZnO nanoparticles embedded membranes could delay biofouling formation without significantly triggering the overall expression/abundance of antibiotic resistance genes (ARGs) and metal resistance genes (MRGs) in biofilm. Furthermore, CuO and ZnO nanoparticles could inhibit the expression of quorum sensing associated genes, resulting in lower quorum sensing signal molecules production. Despite the positive results demonstrated from this study as well as those from others, we recognize that no control strategies are likely to achieve total prevention of anaerobic biofouling. Therefore, the last part of this dissertation focuses on exploring the effects of different foulant layers on antibiotic-resistant bacteria (ARB) and ARGs removal. Our findings suggest both ARB and ARGs could be absorbed by membrane foulant. Transmembrane pressures and the foulant layer synergistically affected ARB removal, but the foulant layer is the main factor that contributed to ARG removal through adsorption. Overall, the collective findings could bring new insights to the anaerobic membrane biofouling phenomenon, and offer pragmatic approaches to minimize biofouling without compromising the post-AnMBR effluent quality.

Our interest in the red alga Delisea pulchra (=D.fimbriata) (Greville) Montagne 1844 (Rhodophyceae, Bonnemaisoniales, Bonnemaisoniaceace) was stimulated by its activity in the biosssays done at Wyeth Pharmaceuticals. Halogenated compounds from D. pulchra interfere with Gram-negative bacterial signaling systems, affect the growth of Gram-positive bacteria, inhibit quorum sensing and swarming motility of marine bacteria (inhibit bacterial communication). They also inhibit surface colonization in marine bacteria and exhibit antifouling properties against barnacle larvae and macroalgal gametes. Chemical investigation of D.pulchra collected near Palmer Station, Antarctica yielded three new dimeric halogenated furanones, pulchralide A-C (41-43), along with previously reported fimbrolide (21), acetoxyfimbrolide (22), hydroxyfimbrolide (23) and halogenated ketone 40. The reported Compounds were characterized by comparison of their 1H and 13C NMR data with that previously published. Pulchralide A-C were characterized by both 1D (1H NMR, 13C NMR, DEPT, 1H-1H COSY) and 2D (gHMQC, gHMBC) NMR techniques, supported by HREIMS/HRESIMS data. The absolute stereochemistry of Pulchralide A was determined by a single crystal X-ray analysis. Significant antimicrobial activity was observed in acetoxyfimbrolide (22) and hydroxyfimbrolide (23), where as pulcharlide A (41) and fimbrolide (21) were weakly active.

Surfaces submerged in marine environments rapidly get colonized by marine organisms, a process known as biofouling. Fouling costs maritime industries billions of dollars annually. The most common methods of combating marine biofouling are toxin containing antifouling coatings which often have detrimental non-target environmental effects. These effects and proposed bans on harmful substances in antifouling coatings, mandates development of more environmentally friendly antifouling technologies. Of these, foul-release coatings, which minimize attachment and adhesion of fouling organisms (rather than killing them) are promising alternatives. Here I explored the utility of petroleum waxes as novel antifouling/foul-release coatings. I first investigated the responses of propagules (larvae or spores) of six common fouling organisms to wax coatings in the laboratory. A wide variation in the response of these different organisms, and in the different types of response (settlement, adhesion, etc.) by the same organism, was observed, but the most inhibitory coatings were those made from microcrystalline wax and silicone oil. However, in field trials in Sydney Harbour, paraffin waxes had the strongest antifouling performance, with activity up to one year (the trial duration). These waxes also had strong foul-release effects, with fouling that did attach mostly removed by a low pressure water jet. Composition of fouling communities on paraffin waxes differed significantly from other waxes or controls, with little or no hard fouling organisms (barnacles, bivalves) on paraffin. The mechanisms of antifouling and foul-release actions of paraffin waxes appear to be due to changes in surface properties. The surfaces of the paraffin waxes changed noticeably after 4 - 8 weeks immersion in the sea or in seawater aquaria. Antibiotic treatments showed that this change in surface appearance was due to biological (microbial) activity. Bacteria appear to remove the amorphous phase from the surface of the paraffin waxes, revealing an underlying crystalline phase, which is less affected by bacterial action. I suggest that these crystals form a microstructured ?bed of nails? of crystals of varying shapes and sizes which inhibit settlement and reduce adhesion strength of those organisms which do settle.

Tout support immergé dans l'eau est rapidement colonisé par de nombreux organismes micro- et macroscopiques. Ce phénomène séquentiel et complexe appelé biofouling est à l'origine de nombreux préjudices économiques et écologiques, notamment dans le milieu marin. L'interdiction récente de certaines substances toxiques, utilisées comme biocides dans les revêtements antifouling des coques de bateaux notamment, a relancé l'intérêt de rechercher de nouvelles molécules antifouling respectueuses de l'environnement. L'objectif de cette thèse a été de développer et d'amorcer l'étude de la représentativité d'un bio-essai permettant d'évaluer le potentiel antifouling de molécules et de revêtements sur des " biofilms " mono et plurispécifiques in vitro en microplaques grâce à l'utilisation de fluorochromes. Le choix a été fait de se focaliser sur le biofilm primaire car il est envisagé que l'élimination ou la limitation de ce dernier réduisent le biofouling. Cinq souches de bactéries marines pionnières, isolées de la Rade de Toulon et en Bretagne, ont été utilisées afin de comparer l'efficacité anti-adhésion de molécules commerciales et naturelles. Deux dérivés de synthèse de substances naturelles marines (TFA E et Z) ont présenté une activité significative associée à une absence de toxicité sur bactéries, suggérant ainsi un mode d'action anti-adhésion spécifique. En outre, les différences de sensibilité entre souches ont confirmée l'importance de réaliser le bio-essai avec un panel diversifié de bactéries.Afin de voir si les données obtenues en laboratoire reflétaient ce qui se produit dans le milieu naturel, une comparaison entre les résultats du bio-essai en microplaque appliqué à six revêtements et les biofilms qui ont colonisés ces mêmes peintures immergées un mois dans la Rade de Toulon (analysés par cytométrie de flux, microscopie et PCR-DGGE), a été effectuée. Les analyses quantitatives ont suggéré une cohérence entre les deux approches même si l'absence de revêtement d'efficacité intermédiaire et le nombre de systèmes testés limite la portée de nos conclusions

In earlier research in our lab, the manipulation of microtubules on gold patterned silicon wafers was achieved by E-beam lithography, Poly (ethylene glycol) self assembled monolayers (PEG-SAMs) and electrophoresis. To develop a technique for delicate single microtubule manipulation, further studies need to be done on PEG-SAMs and electrophoresis. As a foundation of this goal, we examined the electric field in an aqueous solution between two planar electrodes and the compatibility of the antifouling property of PEG-SAMs with the electric field. For this purpose, the distribution of microbeads was analyzed using a Boltzmann distribution. The amount of adsorbed microtubules on a PEG-SAM was examined to test the compatibility of the antifouling property of a PEG-SAM with concomitant exposure to electric field. It is shown that the product of the electric field and the effective charge of the microbead does not have a linear relation with the applied electric potential but an exponentially increasing function with respect to the potential. The antifouling property of the PEG-SAM was not retained after an exposure to the electric field.

Surfaces submerged in marine environments rapidly get colonized by marine organisms, a process known as biofouling. Fouling costs maritime industries billions of dollars annually. The most common methods of combating marine biofouling are toxin containing antifouling coatings which often have detrimental non-target environmental effects. These effects and proposed bans on harmful substances in antifouling coatings, mandates development of more environmentally friendly antifouling technologies. Of these, foul-release coatings, which minimize attachment and adhesion of fouling organisms (rather than killing them) are promising alternatives. Here I explored the utility of petroleum waxes as novel antifouling/foul-release coatings. I first investigated the responses of propagules (larvae or spores) of six common fouling organisms to wax coatings in the laboratory. A wide variation in the response of these different organisms, and in the different types of response (settlement, adhesion, etc.) by the same organism, was observed, but the most inhibitory coatings were those made from microcrystalline wax and silicone oil. However, in field trials in Sydney Harbour, paraffin waxes had the strongest antifouling performance, with activity up to one year (the trial duration). These waxes also had strong foul-release effects, with fouling that did attach mostly removed by a low pressure water jet. Composition of fouling communities on paraffin waxes differed significantly from other waxes or controls, with little or no hard fouling organisms (barnacles, bivalves) on paraffin. The mechanisms of antifouling and foul-release actions of paraffin waxes appear to be due to changes in surface properties. The surfaces of the paraffin waxes changed noticeably after 4 - 8 weeks immersion in the sea or in seawater aquaria. Antibiotic treatments showed that this change in surface appearance was due to biological (microbial) activity. Bacteria appear to remove the amorphous phase from the surface of the paraffin waxes, revealing an underlying crystalline phase, which is less affected by bacterial action. I suggest that these crystals form a microstructured ?bed of nails? of crystals of varying shapes and sizes which inhibit settlement and reduce adhesion strength of those organisms which do settle.

Microorganisms attachment to the surfaces located in the marine water has become a significant problem. Historically, the antifouling properties of the coatings were achieved by using biocides, which had a negative consequence to the marine environment. Currently, alternative environmental friendly methods are required. This thesis aimed to investigate and produce the antifouling coatings that can be used as potential candidates in the marine industry. In this study, a range of novel polymer nanocomposite coatings was fabricated via the method of solvent and tested based on the strategy of microbial adhesion. The composition of the coatings mainly contains polidimethylsiloxane (PDMS) and different nanomaterials. The coatings applied on glass substrate were characterised using X-ray spectroscopy (XRD), scanning electron microscopy (SEM), contact angle measurements, inductively coupled plasma mass spectroscopy (ICP-MS) and atomic force microscopy (AFM). In biofouling assays, attachment of bacteria B. Subtilis and three marine microalgae (Skeletonema sp., Amphora sp., D. Salina) was investigated in laboratory scale. The obtained results suggested that small amount of nanoparticles in the polymer matrix can improve the antifouling settlement behaviour of the coatings. All microalgae attached more on PDMS/SiO2 and control surfaces (glass and PDMS) compared to the coatings containing multiwall carbon nanotubes (MWCNT) and sodium bismuth titanate (NBT). The influence of contact time, surface roughness and surface wettability was also studied. The microbial attachment varied significantly with respect to contact time and surface properties. There was no obvious evidence showing that the wetting properties and the roughness of the coatings have an effect on growth ... [cont.].

Doctora en Ciencias de la Ingeniería, Mención Ciencia de los Materiales / La contaminación de microorganismos produce serios problemas asociados a la transmisión de enfermedades o al deterioro de las superficies a las cuales éstos se adhieren. Las infecciones intrahospitalarias (IIH) generan altas tasas de mortandad y elevados costos para los pacientes. Además, cuando las superficies se exponen a ambientes húmedos, se facilita la adhesión de microorganismos que provocan su ensuciamiento y deterioro, lo que se conoce como biofouling. Mallas plásticas para cultivos acuícolas se ven gravemente afectadas por el biofouling marino, generando altos costos asociados a su remoción. En base a lo anterior, existe una alta demanda de nuevos materiales con actividad antimicrobial y antifouling, en particular los polímeros son de gran interés debido a su fácil procesamiento, y a que pueden sustituir desde superficies hospitalarias a mallas acuícolas. El objetivo del trabajo es desarrollar compósitos poliméricos antimicrobiales y antifouling con la incorporación de diferentes tipos de partículas a base de cobre mediante el método de mezcla en fundido. Se usaron nanopartículas de cobre metálico (NPsCu) y de cobre oxidado (NPsCuO), además de micropartículas de cobre metálico (MPsCu). Se estudió además la dispersión del cobre al ser incorporado soportado o recubierto. Para ello se sintetizaron dos tipos de partículas híbridas: cobre soportado en sílice nanométrica (NPsCu/Si) y cobre funcionalizado superficialmente con cadenas orgánicas (NP Func). La actividad antimicrobial de Polipropileno (PP) fue estudiada en función de la cantidad de nanopartículas y el tiempo de contacto. PP con 5, 10 y 20 %v/v de NPsCu eliminaron en 99,9% de E. coli, S. aureus y P. aeruginosa en menos de 240 min. Los resultados mostraron que la actividad antimicrobial depende del tipo de bacteria e incrementa con el contenido de cobre. La actividad antifouling de PP fue estudiada en función del tipo y cantidad de nanopartículas. PP con 1 a 20%v/v de NPsCu disminuyeron hasta en un 90% el biofouling después de dos meses en el mar, mientras que PP con 1 a 5%v/v de NPsCuO lo redujeron hasta en un 30% en el mismo tiempo. La actividad antimicrobiana y antifouling se relacionó con la capacidad de liberar iones cúpricos (Cu+2). PP con NPsCu logró mayor liberación que con NPsCuO, en las mismas condiciones. Las partículas de cobre funcionalizado con cadenas orgánicas (NP Func) exhibieron buena dispersión en la matriz polimérica, no así las partículas de cobre soportadas (NPsCu/Si). Ambas partículas, puras o embebidas en PP, tienen alta liberación de cobre. La capacidad de liberación de las partículas en base a cobre se incrementa en el siguiente orden: NPsCuO, NPsCu, NPsCu/Si y NP Func. Además, la disminución del tamaño del relleno y el uso de matrices poliméricas hidrófilas o con baja cristalinidad favorecen la liberación. Estos resultados muestras que partículas en base a cobre le confieren propiedades antimicrobiales y antifouling a matrices poliméricas. Estos nuevos materiales tienen la potencialidad de aplicados en superficies hospitalarias como medida complementaría en la prevención de las IIH. También emergen como materiales de reemplazo en la fabricación de mallas acuícolas o estructuras plásticas afectadas por el biofouling marino.

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