>Magister Scientiae - MSc / Membrane separation processes have been widely applied in the treatment of wastewater with polysulfone (PSF) polymer membrane being the most frequently used in ultrafiltration of wastewater due to its chemical and structural stability and mechanical robustness. The disadvantage to these membranes is their hydrophobicity which leads to membrane fouling caused by organic pollutants in water. Many studies have been conducted to increase the hydrophilic properties of the polysulfone membrane surface. Most recently metal oxide nanoparticles have been introduced to the polymer matrix in order to reduce membrane fouling and increase its hydrophilicity with measurable success. Natural organic matters are the one of the major fouling agents during ultrafiltration, reverse osmosis and microfiltration. Two organic acids (Tannic Acid and Alginic Acid) were selected to test the fouling behaviour of nanometallic synthesised polysulfone membranes. For this study, polysulfone casting suspension was prepared by dissolving polysulfone beads in N,N-dimethly acetamide. Three metallic nanoparticles of Silver, Cobalt and Nickel were selected to improve the hydrophilicity of the polysulfone membrane. The metal nanoparticles were prepared using the chemical reduction method. Cobalt nanoparticles were synthesized by dissolving the cobalt chloride salt in deionized water and reduced with sodium borohydride at room temperature. The nickel chloride salt was dissolved in ethanol and reduced with sodium borohydride under magnetic stirrer. Silver nanoparticles were prepared by dissolving the silver nitrate in deionised water and heated to boil, the sodium citrate was added to reduced the silver nitrate. These nanoparticles were then integrated into the polysulfone polymer matrix to form the metal nanoparticle polysulfone nanocomposites. This study focused on four prepared polysulfone nanocomposite membrane; 1 unmodified polysulfone (PSF), 2 polysulfone modified with cobalt nanoparticles (PSF/Co), 3 polysulfone modified with nickel nanoparticles (PSF/Ni) and 4 polysulfone modified with silver nanoparticles (PSF/Ag).

Due to the immuncompromised status of AIDS patients, secondary infections and malignancies are common. Conditions secondary to AIDS for which patients require treatment include Karposi's sarcoma (treated with methotrexate), varicella-zoster (treated with antivirals such as acyclovir) and herpes simplex (also treated with antivirals like acyclovir or idoxuridme). However the clinical efficacy of these drugs is limited by poor skin permeability. Few reports, however, have dealt with the delivery of low molecular weight hydrophilic drugs from these vesicles (El Maghraby et al, 2000). The aim of our study was to investigate in vitro permeation of methotrexate, acyclovir and idoxuridine across human epidermal membrane from elastic liposomes. The intent was to establish whether formulation of these hydrophilic drugs into elastic liposomes would enhance their skin permeation parameters. We developed and validated high-performance liquid chromatographic techniques for quantitative analysis of methotrexate, idoxuridine and acyclovir. Elastic liposomes were prepared from various phospholipids- phosphatidylcholine 78.6%; phosphatidylcholine 50%; hydrogenated phosphatidylcholine 90%; phosphatidylcholine 95% and surfactants - sodium cholate, sodium deoxycholate, Span 20, 40, 60, 80. These vesicles were characterised by transmission electron microscopy. The solubilities of methotrexate, acyclovir and idoxuridine were determined. Phospholipon G (95% phosphatidylcholine) was chosen for the preparation of the liposomes with different surfactants. Permeation of methotrexate, acyclovir and idoxuridme from these vesicles across human epidermal membrane was investigated. Flux values for methotrexate, acyclovir and idoxuridine values (J) obtained by curve-fitting of data using Easyplot were compared to those obtained by linear regression. We used Student's t-test to determine statistically significant differences in the flux values of the formulations. A computer program http://www.physics.csbsju.edu/stats/ttest- bulk-form.html was used for this purpose. Our results indicate that there are no statistically significant differences between flux values from elastic liposomes and saturated aqueous solutions. / Thesis (Ph.D. (Pharmaceutics))--North-West University, Potchefstroom Campus, 2004.

Due to the immuncompromised status of AIDS patients, secondary infections and malignancies are common. Conditions secondary to AIDS for which patients require treatment include Karposi's sarcoma (treated with methotrexate), varicella-zoster (treated with antivirals such as acyclovir) and herpes simplex (also treated with antivirals like acyclovir or idoxuridme). However the clinical efficacy of these drugs is limited by poor skin permeability. Few reports, however, have dealt with the delivery of low molecular weight hydrophilic drugs from these vesicles (El Maghraby et al, 2000). The aim of our study was to investigate in vitro permeation of methotrexate, acyclovir and idoxuridine across human epidermal membrane from elastic liposomes. The intent was to establish whether formulation of these hydrophilic drugs into elastic liposomes would enhance their skin permeation parameters. We developed and validated high-performance liquid chromatographic techniques for quantitative analysis of methotrexate, idoxuridine and acyclovir. Elastic liposomes were prepared from various phospholipids- phosphatidylcholine 78.6%; phosphatidylcholine 50%; hydrogenated phosphatidylcholine 90%; phosphatidylcholine 95% and surfactants - sodium cholate, sodium deoxycholate, Span 20, 40, 60, 80. These vesicles were characterised by transmission electron microscopy. The solubilities of methotrexate, acyclovir and idoxuridine were determined. Phospholipon G (95% phosphatidylcholine) was chosen for the preparation of the liposomes with different surfactants. Permeation of methotrexate, acyclovir and idoxuridme from these vesicles across human epidermal membrane was investigated. Flux values for methotrexate, acyclovir and idoxuridine values (J) obtained by curve-fitting of data using Easyplot were compared to those obtained by linear regression. We used Student's t-test to determine statistically significant differences in the flux values of the formulations. A computer program http://www.physics.csbsju.edu/stats/ttest- bulk-form.html was used for this purpose. Our results indicate that there are no statistically significant differences between flux values from elastic liposomes and saturated aqueous solutions. / Thesis (Ph.D. (Pharmaceutics))--North-West University, Potchefstroom Campus, 2004.

Την τελευταία δεκαετία, η επεξεργασία υφασμάτων με πλάσμα έχει αποκτήσει μεγάλο τεχνολογικό ενδιαφέρον καθώς μπορεί να χρησιμοποιηθεί σε διάφορα στάδια της επεξεργασίας. Η οξείδωση της επιφάνειας, η ενίσχυση της υδροφιλίας ή της υδροφοβικότητας της και η αντιμικροβιακή δράση, είναι κάποια παραδείγματα τέτοιων εφαρμογών. Τα πλεονεκτήματα της τεχνικής του πλάσματος σε σύγκριση με άλλες τεχνικές είναι ότι είναι φιλική προς το περιβάλλον και ταυτόχρονα οικονομική αφού μειώνει τις απαιτήσεις σε νερό και ενέργεια. Παρόλα αυτά δεν υπάρχουν στη βιβλιογραφία επαρκείς μελέτες σχετικά με τους βασικούς μηχανισμούς που διέπουν τη διεργασία. Σε αυτή την κατεύθυνση επικεντρώσαμε στη μελέτη της επίδρασης του πλάσματος He/O2 σε χαμηλές πιέσεις με στόχο την ενίσχυση της υδροφιλίας της επιφάνειας, στη διερεύνηση της επίδρασης του C2F6 πλάσματος για την ενίσχυση της υδροφοβικότητας καθώς και στο σχηματισμό PEO-like υμενίων για την βελτίωση της αντιμικροβιακής δράσης της επιφάνειας. Πιο συγκεκριμένα, μελετήθηκε η επίδραση του ποσοστού οξυγόνου στο μείγμα του αερίου, του χρόνου επεξεργασίας, της συνολικής πίεσης και της ισχύος του πλάσματος στην μεταβολή των επιφανειακών ιδιοτήτων και κυρίως στην ενίσχυση της υδροφιλικότητας πολυεστερικών υφασμάτων πριν και μετά από το αποκολλάρισμα τους. Για τη μελέτη της υδροφοβικότητας πραγματοποιήθηκαν πειράματα ως προς την συνολική πίεση, το χρόνο διεργασίας και την απόσταση των ηλεκτροδίων. Τέλος, για την ενίσχυση της αντιμικροβιακής δράσης της επιφάνειας μελετήθηκε η συνολική πίεση, η ισχύς καθώς και το ποσοστό του οξυγόνου στο μίγμα. Οι αλλαγές που λαμβάνουν χώρα στην αέρια φάση και ο πιθανότερος μηχανισμός στον οποίο οφείλονται οι αλλαγές στην επιφάνεια του υποστρώματος μελετήθηκαν με την εφαρμογή διαγνωστικών τεχνικών του πλάσματος. Έτσι ηλεκτρικές μετρήσεις πραγματοποιήθηκαν για τον υπολογισμό της καταναλισκόμενης ισχύος και της εμπέδησης της εκκένωσης ενώ παράλληλα, πραγματοποιήθηκαν οπτικές μετρήσεις με στόχο την καταγραφή των ειδών που παράγονται στην εκκένωση και την κατανομή τους στον χώρο. Από την άλλη μεριά για τη μελέτη των δομικών και φυσικοχημικών μεταβολών που υφίσταται η επιφάνεια κατά την επεξεργασία της με πλάσμα χρησιμοποιήθηκαν ηλεκτρονιακή μικροσκοπία σάρωσης και φασματοσκοπία φωτοηλεκτρονίων από ακτίνες Χ. Τέλος, μετρήσεις του ρυθμού απορρόφησης σταγόνας, γωνίες αδιαβροχίας και προσρόφηση πρωτεϊνών χρησιμοποιήθηκαν ως μέτρο εκτίμησης της υδροφιλίας, της υδροφοβικότητας και της αντιμικροβιακής δράσης αντίστοιχα. Τα βέλτιστα αποτελέσματα παρουσιάζονται και συζητούνται σαν συνάρτηση των ιδιοτήτων του πλάσματος / The last decade, the treatment of polyester textiles using plasma techniques has gained a lot of technological interest. The surface oxidation, the enhancement of hydrophilicity/hydrophobicity and the deposition of antibacterial films are examples of technological plasma applications. The benefits of using the plasma techniques are enormous. The major ones are that is an environmental friendly method and at the same time is economical due to the reduction of energy and water consumption. Although, in the bibliography there are not sufficient studies relevant to the basic mechanism of the plasma treatment/deposition. In this direction, we focused our study on the effect of plasma He/O2 treatment in low values of pressure, targeting the enhancement of surface hydrophilicity, on the deposition conditions of Teflon-like and peo-like films, targeting the enhancement of hydrophobicity and antibacterial effect respectively. In more details, it was examined the effect of oxygen percentage in He/O2 mixture, the discharge time, the total pressure and the power in the alteration of surface properties. Furthermore, experiments were implemented in different pressure, discharge time, power and distance electrode conditions in order to achieve better hydrophobicity. At last, as far as the deposition of peo-like coatings were concerned, power, pressure and oxygen percentage were parameters under investigation. The alterations which took place in the gas phase and the most possible treatment/deposition mechanism were studied using diagnostic techniques such as electrical and optical measurements. On the other hand, for the investigation of physicochemical alterations on the surface, measurements such as xps, water droplet absorption and WCA were implemented. The best results are presented and are discussed as a function of plasma properties.

Membrane bioreactors (MBRs) offer promising solution for wastewater treatment and reuse to address the problem of water scarcity. Nevertheless, this technology is still facing challenges associated with membrane biofouling. This phenomenon has been mainly investigated in lab-scale MBRs with little or no insight on biofouling in full-scale MBR plants. Furthermore, the temporal dynamics of biofouling microbial communities and their extracellular polymeric substances (EPS) are less studied. Herein, a multidisciplinary approach was adopted to address the above knowledge gaps in lab- and full-scale MBRs. In the full-scale MBR study, 16S rRNA gene pyrosequencing with multivariate statistical analysis revealed that the early and mature biofilm communities from five full-scale MBRs differed significantly from the source community (i.e. activated sludge), and random immigration of species from the source community was unlikely to shape the community structure of biofilms. Also, a core biofouling community was shared between the five MBR plants sampled despite differences in their operating conditions. In the lab-scale MBR studies, temporal dynamics of microbial communities and their EPS products were monitored on different hydrophobic and hydrophilic membranes during 30 days. At the early stages of filtration (1 d), the same early colonizers belonging to the class Betaproteobacteria were identified on all the membranes. However, their relative abundance decreased on day 20 and 30, and sequence reads belonging to the phylum Firmicutes and Chlorobi became dominant on all the membranes on day 20 and 30. In addition, the intrinsic membrane characteristic did not select any specific EPS fractions at the initial stages of filtration and the same EPS foulants developed with time on the hydrophobic and hydrophilic membranes. Our results indicated that the membrane surface characteristics did not select for specific biofouling communities or EPS foulants, and the same early colonizers were selected from the source community (i.e. activated sludge), and then went through significant changes to form a mature biofilm. Our findings from these studies could support future research aimed at developing enhanced biological-based strategies to control biofouling in MBRs.

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Made available in DSpace on 2017-07-24T19:38:03Z (GMT). No. of bitstreams: 1 Elementos pre textuais.pdf: 126219 bytes, checksum: a4c1ca3bb1afd43046bbfa4177592e32 (MD5) Previous issue date: 2010-02-26 / There is a considerable interest in the synthesis of water soluble porphyrins due to its use as models of biological systems, as drugs and as homogeneous catalysts in aqueous media. Within this context, this work describes the synthesis of meso-tetraphenylporphyrins with reactive groups on the meso-phenyl ring to generate trimethylarylammonium salts derivatives, resulting in cationic porphyrins with hydrophilic character. Thus, it was obtained iodide salts of 4-TMA-TPP 13 by the complete alkylation of 4-DMA-TPP 15 (91% yield), and 4-NH2-TPP 12 using 2,6-lutidine (69% yield). The synthesis of porphyrins 2-NO2-TPP 16, 2-NH2-TPP 17, 4-NO2-TPP 14, 4-NH2-TPP 12 and 4-DMA-TPP 15 were also studied. The methods described in the literature for the synthesis of 2-NO2-TPP 16 and 4-NO2-TPP 14 were optimized, and the yield (40%) of for 2-NO2-TPP 16 was higher than those reported in the literature (5% overall yield). Porphyrins 17 and 12 were obtained by reduction of 16 and 14, respectively, using concentrated hydrochloric acid and tin (II) chloride dihydrate, without requiring an inert atmosphere. The method was improved, thus facilitating the isolation and purification steps. The synthesis of 4-DMA-TPP 15 was performed using both Adler-Longo method (5% yield) and a modification of Adler’s method, using 1:1 mixture of propionic and octanoic acids (7,0% yield). The porphyrins were fully characterized by infrared, UV-Vis and RMN spectroscopies. All the spectral data were consistent with those reported in the literature. / Há considerável interesse na síntese de porfirinas aquossolúveis devido à possibilidade de usá-las como modelos de sistemas biológicos, como drogas e como catalisadores homogêneos em meio aquoso. Dentro deste contexto, este trabalho descreve a síntese de meso-tetrafenilporfirinas com substituintes reativos no anel meso-fenila para obtenção de derivado porfirínico catiônico, resultando em porfirinas com caráter hidrofílico. Assim, obtivemos sais de iodeto de 4-TMA-TPP 13 a partir da metilação de 4-DMA-TPP 15, com rendimento de 91%, e a partir da metilação de 4-NH2-TPP 12, usando 2,6-lutidina, com rendimento de 69%. A reação de obtenção das porfirinas 2-NO2-TPP 16, 2-NH2-TPP 17, 4-NO2-TPP 14, 4-NH2-TPP 12 e 4-DMA-TPP 15 também foram estudadas. Os métodos descritos na literatura para a síntese da 2-NO2-TPP 16 e 4-NO2-TPP 14 foram alterados para facilitar e otimizar as etapas de isolamento e purificação. Para a 2-NO2-TPP 16 obteve-se rendimento de 40%, superior aos 5% descritos em literatura. As amino-porfirinas 17 e 12 foram obtidas por redução de 14 e 16, respectivamente, utilizando-se ácido clorídrico concentrado e cloreto de estanho (II) dihidratado e, sem a necessidade de atmosfera inerte. O método foi assim simplificado, facilitando as etapas de isolamento e purificação. A síntese da 4-DMA-TPP 15 foi a partir do método Adler-Longo, com rendimento de 5,0%, e a partir do método de Adler-Longo modificado em que utilizou-se como solvente uma mistura 1:1 de ácido propanóico e octanóico, com rendimento de 7,0%. As porfirinas sintetizadas foram caracterizadas por espectrometria na região do infravermelho (IV), do ultravioleta e visível (UV-Vis) e por ressonância magnética nuclear (RMN) de H1 e C13. Os dados espectrais obtidos estão de acordo com os descritos na literatura.

Le projet NEOPHIL a pour ambition d'élaborer une membrane d'ultrafiltration (UF) en fibre creuse de poly(fluorure de vinylidène) (PVdF) possédant une résistance au colmatage stable dans le temps. Cette propriété peut être acquise par l'ajout d'un copolymère à blocs nommé GEN dans la solution de préparation des fibres en plus de l'additif poly(vinyl pyrrolidone) (PVP) classiquement utilisé. Dans ce travail, nous nous sommes attachés à la détermination des additifs en surface, dans la masse et à établir des profils de concentration par ATR-FTIR, T%-FTIR et microscopie Raman. Ces analyses ont montré que la moitié de la PVP est lessivée dans le bain de coagulation alors que GEN reste quantitativement ancré dans la matrice. Dans le cas de la PVP, les paramètres d'élaboration comme la présence de solvant ou de PVP dans le bain de coagulation influent fortement sur le profil de concentration au niveau des interfaces. Par la suite, une analyse multicritère entre l'hydrophilie apportée par les additifs et le colmatage a été effectuée. Cette étude a été réalisée par des mesures d'angle de contact à l'eau, de rétention d'eau et de pression d'intrusion d'eau sur fibres sèches en relation avec la taille et la distribution des pores, la rugosité de surface (AFM) et la perméabilité à l'eau pure. La rétention d'eau et la pression d'intrusion d'eau semblent les deux techniques les plus pertinentes pouvant relier les propriétés physico-chimiques et les performances de filtration. Une étude préliminaire sur le comportement au vieillissement a également été effectuée qui montre que GEN est peu extrait alors que la PVP disparait en partie par extraction et/ou dégradation. Ce phénomène affecte fortement les différents paramètres étudiés dans l'analyse multicritère. / The project NEOPHIL aims to develop an ultrafiltration (UF) membrane hollow fiber from poly (vinylidene fluoride) (PVdF) that resists to fouling amide time. This property can be achieved by adding a block copolymer called GEN in the fiber preparation solution in addition to the classic additive, poly (vinyl pyrrolidone) (PVP). In this work, we focused on the quantification of additives on the surface, in the bulk and establishing the concentration profile by ATR-FTIR, T% -FTIR and Raman microscopy. These analyzes showed that half of the PVP is washed away into the coagulation bath while GEN quantitatively remains anchored in the matrix. In the case of PVP, the formulation parameters such as the presence of solvent or PVP in the coagulation bath greatly affects the concentration profile at the interfaces. In addition a multi-criteria analysis between hydrophilicity provided by the additives and the fouling was established. This study was carried out by measurement of the water contact angle, water retention and water intrusion pressure of dry fibers in relation to the size and distribution of pores, the surface roughness (AFM) and the permeability to pure water. Water retention and water intrusion pressure seem to be the two most relevant techniques that can connect the physicochemical properties and filtration performance. A preliminary study on the aging behavior was also performed showing that GEN is not extracted while the PVP is lost partly by extraction and/or degradation. This phenomenon strongly affects the different parameters studied in the multi-criteria analysis.

This study demonstrates that the surface motility of the bacterium Pseudomonas aeruginosa is dependent on the surface chemistry of the underlying substrate. In particular, cells on hydrophobic polydimethylsiloxane (PDMS) have a speed that is on average 38% greater than on hydrophilic PDMS. These results were obtained using time-lapse microscopy of bacteria exposed to continuously flowing tryptic soy broth growth medium at 37 ⁰C. Not only are the mean speeds different, the distributions of speeds are also different: on the hydrophobic substrate, a smaller proportion of bacteria move by less than about one body-length (~3 µm) in 60 minutes. In addition, the surface chemistry affects the orientation of the cells: there is a greater fraction of "walking" bacteria on the hydrophobic surface. Sensitivity to the substrate surface chemistry occurs despite the presence of a complex mix of substances in the growth medium and offers hope that surface chemistry can be used to tune motility and the progression to biofilm formation. Additionally, the effect of reducing the near-surface Young's modulus of the PDMS from 7000 to 70 kPA is investigated. For the lower modulus material, there is an increase in the likelihood of a bacterium executing sudden, high angle turns. This is evident in images with a framerate of one frame per 0.22s. However, the impact of these turns is averaged out over longer times such that the mean speed over periods of more than about one minute is the same for bacteria on both the high and the low modulus materials. Consequently, except over very short time intervals, Young's modulus in the surface region is not effective as a means of modulating motile behavior. / Master of Science / This study demonstrates that the ability of the bacterium Pseudomonas aeruginosa to move on a solid surface is dependent on the surface chemistry of the underlying substrate. In particular, cells on hydrophobic polydimethylsiloxane (PDMS) have a speed that is on average 38% greater than on hydrophilic PDMS. These results were obtained using time-lapse microscopy of bacteria exposed to continuously flowing growth medium at 37 ⁰C. Not only are the mean speeds different, the distributions of speeds are also different: on the hydrophobic substrate, a smaller proportion of bacteria move by less than about one body-length (~3 µm) in 60 minutes. In addition, the surface chemistry affects the orientation of the cells: there is a greater fraction of vertically-oriented bacteria on the hydrophobic surface. Additionally, the effect of reducing the stiffness of the PDMS from 7000 to 70 kPA is investigated. For the less stiff material, there is an increase in the likelihood of a bacterium executing sudden, high angle turns. This is evident in images with a framerate of one frame per 0.22s. However, the impact of these turns is averaged out over longer times such that the mean speed over periods of more than about one minute is the same for bacteria on both the high and the low stiffness materials. Consequently, except over very short time intervals, stiffness in the surface region is not effective as a means of changing patterns of surface-bound P. aeruginosa movement.