Dynamic and interaction of cytochrome c with Pf1 virus

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em BioOrgânica

Role of surfactants in filtration and fouling of colloidal silica

The EM3E Master is an Education Programme supported by the European Commission, the European Membrane Society (EMS), the European Membrane House (EMH), and a large international network of industrial companies, research centres and universities

Bioremediation of diesel contaminated soils : an investigation into the effects of biosurfactant and organic matter amendments

The aim of this study was to investigate the effects of biosurfactants and organic matter amendments on the bioremediation of diesel contaminated soil. Two strains of Pseudomonas aeruginosa with the ability to produce biosurfactant were isolated from a water and soil sample in Co. Sligo. The first strain, Isolate A, produced a biosurfactant which contained four rhamnose containing compounds, when grown in proteose peptone glucose ammonium salts medium with glucose as the carbon source. Two of the components were identified as rhamnolipid 1 and 2 whilst the other two components were unidentified. The second strain, Isolate GO, when grown in similar conditions produced a biosurfactant which contained only rhamnolipid 2. The type of aeration system used had a significant effect on the abiotic removal of diesel from soil. Forced aeration at a rate of 120L 02/kg soil/ hour resulted in the greatest removal. Over a 112 day incubation period this type o f aeration resulted in the removal o f 48% o f total hexane extractable material. In relation to bioremediation of the diesel contaminated sandy soil, amending the soil with two inorganic nutrients, KH2PO4 and NÜ4N03, significantly enhanced the removal of diesel, especially the «- alkanes, when compared to an unamended control. The biosurfactant from Isolate A and a biosurfactant produced by Pseudomonas aeruginosa NCIMB 8628 (a known biosurfactant producer), when applied at a concentration of three times their critical micelle concentration, had a neutral effect on the biodégradation o f diesel contaminated sandy soil, even in the presence o f inorganic nutrients. It was deduced that the main reason for this neutral effect was because they were both readily biodegraded by the indigenous microorganisms. The most significant removal of diesel occurred when the soils were amended with two organic materials plus the inorganic nutrients. Amendment of the diesel contaminated soil with spent brewery grain (SBG) removed significantly more diesel than amendment with dried molassed sugar beet pulp (DMSBP). After a 108 day incubation period, amendment of the diesel contaminated soil with DMSBP plus inorganic nutrients and SBG plus inorganic nutrients resulted in 72 and 89% removal of diesel range organics (DRO), in comparison to 41% removal of DRO in an inorganic nutrient amended control. The first order kinetic model described the degradation of the different diesel components with high correlation and was used to calculate Vi lives. The V2 life, of the total «-alkanes in the diesel was reduced from 40 days in the control to 8.5 and 5.1 days in the presence of DMSBP and SBG, respectively. The V2 life o f the unresolved complex mixture (UCM) in the diesel contaminated soil was also significantly reduced in the presence o f the two organics. DMSBP and SBG addition reduced UCM V2 life to 86 and 43 days, respectively, compared to 153 days in the control. The component of diesel whose removal was enhanced the greatest through the organic material amendments was the isoprenoid, pristane, a compound which until recently was thought to be nonbiodegradable and was used as an inert biomarker in oil degradation studies. The V2 life of pristane was reduced from 533 days in the nutrient amended control to 49.5 and 19.5 days in DMSBP and SBG amended soils. These results indicate that the addition o f the DMSBP and SBG to diesel contaminated soil stimulated diesel biodégradation, probably by enhancing the indigenous diesel degrading microbial population to degrade diesel hydrocarbons, whilst the addition o f biosurfactants had no enhanced effect on the bioremediation process.

Estudi de la desadsorció del pirè amb diferents surfactants en tres sòls artificials

Un dels problemes associats a la remeiació de contaminants hidròfobs és la seva poca disponibilitat. Es considera que un contaminant està disponible quan roman a la fase líquida del medi, ja sigui solubilitzat o en forma d’emulsió. Els surfactants són substàncies anfifíliques que promouen la transferència de compostos hidròfobs de la fase sòlida a la líquida. En aquest estudi s’escull el pirè com a representant dels hidrocarburs aromàtics policíclics i tres surfactants no iònics: un àmpliament citat a la bibliografia científica (Tween 80) i dos comercials (Gold Crew, BS-400). L’estudi es fa amb tres mescles d’argila i sorra amb diferents proporcions. La concentració micel·lar crítica (CMC) s’assoleix abans en sòls amb poc contingut en argila. L’eficiència dels surfactants està estretament relacionada amb la proporció d’argila i sorra. A concentracions molt per sobre de la CMC no s’observa una relació entre l’eficiència i la quantitat d’argila. El Tween 80 ha donat millors resultats que el Gold Crew i el BS-400, sense que aquest darrer no hagi presentat desadsorció de pirè.

Eräiden paperinvalmistuksessa käytettävien vahadispersioiden stabiilisuuden hallinta

Diplomityön tavoitteena oli selvittää millainen laaduntarkastus AKD-dispersioille tulisi suorittaa kuormien vastaanotossa ja tulisiko dispersioiden laatu tarkastaa uudelleen ennen annostelua. Tätä varten seurattiin toimituserien laadun tasaisuutta ja tarkasteltiin varastointiolosuhteiden vaikutusta dispersioiden säilyvyyteen. Lisäksi kartoitettiin dispersioiden käsittelyssä ja kartonginvalmistusprosessissa esiintyvien riskitekijöiden vaikutuksia kaupallisten dispersioiden stabiilisuuteen. Kirjallisuusosassa perehdyttiin kolloidisiin dispersioihin sekä niiden stabiilisuuteen vaikuttaviin tekijöihin. AKD-dispersiot valmistetaan emulgointitekniikoiden avulla, joten dispergointimenetelmien ohella käsiteltiin myös emulsioiden valmistamista. Lisäksi luotiin katsaus dispersioteknologian tärkeimpiin analyysimenetelmiin. Alkyyliketeenidimeerin osalta käsiteltiin emulgoinnin lisäksi vahan ja muiden lisäaineiden vaikutuksia dispersioiden stabiilisuuteen ja myös niiden merkitystä dispersioiden formuloinnissa. AKD-liimauksen osalta esiin tuotiin AKD:n tärkeimmät reaktiomekanismit, sillä ne liittyvät osittain myös dispersioiden stabiilisuuteen. Lopuksi luotiin lyhyt katsaus AKD-dispersioiden stabiilisuutta käsittelevään tutkimukseen, jota on toistaiseksi julkaistu varsin niukasti. Kokeellisessaosassa tarkastelun kohteeksi valittiin neljä kaupallista alkyyliketeenidimeerinvesidispersiota, joiden koostumus ja ominaisuudet selvitettiin perusteellisesti. Tarkoituksena oli auttaa ymmärtämään dispersioiden stabiilisuudessa mahdollisesti esiintyviä eroja. Laajamittainen dispersioiden karakterisointi näyttää olevan tarpeen ainakin otettaessa uutta AKD-laatua käyttöön, sillä dispersioiden koostumus ja ominaisuudet voivat vaihdella merkittävästi. AKD-dispersioiden laadussa esiintyi vaihtelua eri toimituserien välillä. Suurimmat vaihtelut havaittiin dispersioiden varaustiloissa ja partikkelikokojakaumissa. Laadun epätasaisuuden vuoksi vastaanottotarkastuksen merkitys korostuu. Vastaanottotarkastuksessa syytä olisi kiinnittää dispersion kuiva-ainepitoisuuden ohella sen viskositeettiin, varaustilaan, tehoainepitoisuuteen sekä rakenteeseen. Rakenteen tarkastelussa optinen mikroskooppi voi rutiininomaisessa seurannassa korvata partikkelikokojakauman määrittämisen. Varastointilämpötilan vaikutus dispersioidenlaatuun on merkittävä. Dispersiot säilyvät parhaiten viileässä, joten jos varastosäiliöissä ei ole jäähdytystä, on dispersioiden laadun tarkastus tarpeen myös ennen annostelua. Jotta dispersion kunnosta saadaan luotettava arvio, on viskositeetin määrittämiseen yhdistettävä vähintään rakenteen tarkastelu optisella mikroskoopilla. Mekaaninen rasitus voi dominoivasta stabilointimekanismistariippuen aiheuttaa dispersiossa hienoaineen muodostumista tai partikkelien flokkaantumista. Stabilointimekanismi vaikuttaa niin ikään partikkelien käyttäytymiseen korkeissa lämpötiloissa. Dispersioiden stabiilisuuden todettiin heikkenevän pH:n kohotessa emäksiselle alueelle. Elektrolyyttikonsentraatio vaikuttaa partikkelien mikroelektroforeettiseen ioniliikkuvuuteen merkittävästi. Kartonkikoneen märkäosan kemikaaleista anionisen retentioaineen (BMA) todettiin vuorovaikuttavan kationisten AKD-partikkelien kanssa selvimmin. Mikroelektroforeettisen ioniliikkuvuuden mittaaminen kiertovedessä todettiin tärkeäksi, sillä se kuvaa dispersion käyttäytymistä sen käyttöympäristössä.

STYREENI-BUTADIEENILATEKSIN VALMISTUS EMULSIOPOLYMEROIN-NILLA JA LATEKSIN VISKOSITEETTIIN VAIKUTTAVAT TEKIJÄT.

Työn tavoitteina oli kirjallisuusosassa selvittää emulsiopolymeroinnin perusperiaatteet ja lateksien viskositeettiin vaikuttavat tekijät. Kokeellisessa osassa selvitettiin eräiden kaupallisten lateksien viskositeettiin vaikuttavia tekijöitä. Tutkittujen kaupallisten lateksien viskositeettien riippuvuudelle kuiva-ainepitoisuudesta saatiin tulokset, jotka ovat melko hyvin yhtäpitäviä kirjallisuudesta saatujen tulosten kanssa. Tutkitut lateksit erosivat lähinnä maksimaalisen polymeeripartikkelin tilavuusosuuden kohdalla kirjallisuudesta saaduista arvoista. Tämän todettiin johtuvan sähköisen kaksoiskerroksen ja partikkelin pintaan kiinnittyneiden ryhmien vaikutuksesta. Tämä tulos varmentui elektrolyyttipitoisuuden vaikutusta selvitettäessä. Elektrolyyttilisäys laski lateksien viskositeetteja ja pienensi lateksien välisiä viskositeettieroja. Lateksin pH:n nostolla oli selvästi viskositeettia kasvattava vaikutus. Tämä johtuu osaltaan myös sähköisen kaksoiskerroksen kasvamisesta happoryhmien ionisoituessa. Latekseja toisiinsa verrattaessa havaittiin selkeästi karboksyylihapon ja initiaattorista peräisin olevien happoryhmien määrän vaikutus lateksin viskositeetin muutokselle. Paljon karboksyylihappoa ja initiaattoria sisältävien lateksien viskositeetti muuttui selvästi voimakkaammin pH:n muuttuessa. Latekseissa havaittiin myös ero heikkojen karboksyylihapporyhmien ja vahvojen initiaattorista peräisin olevien happoryhmien ionisoitumisen välillä. Vahvat happoryhmät ionisoituivat matalammassa pH:ssa kuin vahvat ja nostavat näin myös viskositeettia matalammassa pH:ssa kuin karboksyylihapporyhmät. Anionisen emulgaattorin lisäyksellä ei havaittu olevan kovinkaan suurta vaikutusta viskositeettiin. Partikkelikoon vaikutusta voitiin tutkia ainoastaan prosessista saadun mittausaineiston avulla. Partikkelikoon vaikutukset peittyivät suurelta osin muiden tekijöiden alle. Ainoastaan yhdelle lateksityypille saatiin selkeä riippuvuus partikkelikoon ja viskositeetin välille. Riippuvuus noudattaa kirjallisuudesta saatuja tietoja eli partikkelikoon kasvaessa viskositeetti laskee. Myös lateksin viskositeetin riippuvuus käytetystä leikkaus-nopeudesta noudattaa hyvin kirjallisuudesta saatuja tuloksia. Lateksin viskositeetti laskee leikkausnopeuden kasvaessa.

Nutrient signature of Quebec (Canada) cranberry (Vaccinium macrocarpon Ait.)

Fertilizer recommendations for cranberry crops are guided by plant and soil tests. However, critical tissue concentration ranges used for diagnostic purposes are inherently biased by nutrient interactions and physiological age. Compositional data analysis using isometric log ratios (ilr) of nutrients as well as time detrending can avoid numerical biases. The objective was to derive unbiased nutrient signature standards for cranberry in Quebec and compare those standards to literature data. Field trials were conducted during 3 consecutive years with varying P treatments at six commercial sites in Quebec. Leaf tissues were analyzed for N, P, K, Ca, Mg, B, Cu, Zn, Mn and Fe. The analytical results were transformed into ilr nutrient balances of parts and groups of parts. High-yield reference ilr values were computed for cranberry yielding greater than 35 Mg ha-1. Many cranberry fields appeared to be over-supplied with K and either under-supplied with Mn or over-supplied with Fe as shown by their imbalanced [K | Ca, Mg] and [Mn | Fe] ratios. Nutrient concentration ranges from Maine and Wisconsin, USA, were combined into ilr values to generate ranges of balances. It was found that these nutrient ranges were much too broad for application in Quebec or outside the Quebec ranges for the [Ca | Mg] and the [Mn | Fe] balances, that were lower compared to those of high yielding cranberry crops in Quebec.

Discrepancies over the onset of surfactant monomer aggregation interpreted by fluorescence, conductivity and surface tension methods

Molecular probe techniques have made important contributions to the determination of microstructure of surfactant assemblies such as size, stability, micropolarity and conformation. Conductivity and surface tension were used to determine the critical aggregation concentration (cac) of polymer-surfactant complexes and the critical micellar concentration (cmc) of aqueous micellar aggregates. The results are compared with those of fluorescent techniques. Several surfactant systems were examined, 1-butanol-sodium dodecylsulfate (SDS) mixtures, solutions containing poly(ethylene oxide)-SDS, poly(vinylpyrrolidone)-SDS and poly(acrylic acid)-alkyltrimethylammonium bromide complexes. We found differences between the cac and cmc values obtained by conductivity or surface tension and those obtained by techniques which use hydrophobic probe.

Interação tensoativo/hidrótropo em sistemas aquosos, utilizando ressonância magnética nuclear de ¹H e 13C

In this work, it was studied the behavior of the nonionic surfactant aqueous solutions, containing or not a hydrotropic agent, by resonance magnetic nuclear (NMR). We have studied monofunctional diblock copolymers of poly(propylene oxide-ethylene oxide) (R-PPO-PEO-OH, where R length is linear C4) as nonionic surfactant and sodium p-toluenesulfonate (NaPTS) as hydrotropic agent. The critical micelle concentration (CMC) of the aqueous copolymer solution was obtained from ¹H-NMR. The preliminary study of the interaction between the copolymer, under the unimer and micelle forms, and the hydrotrope, in aqueous solutions, was evaluated by ¹H-NMR and 13C-NMR.

Reaction Kinetics and Viscosity Modelling in the Fusion Syntheses of Ca- and Ca/Mg-resinates

Rosin is a natural product from pine forests and it is used as a raw material in resinate syntheses. Resinates are polyvalent metal salts of rosin acids and especially Ca- and Ca/Mg- resinates find wide application in the printing ink industry. In this thesis, analytical methods were applied to increase general knowledge of resinate chemistry and the reaction kinetics was studied in order to model the non linear solution viscosity increase during resinate syntheses by the fusion method. Solution viscosity in toluene is an important quality factor for resinates to be used in printing inks. The concept of critical resinate concentration, c crit, was introduced to define an abrupt change in viscosity dependence on resinate concentration in the solution. The concept was then used to explain the non-inear solution viscosity increase during resinate syntheses. A semi empirical model with two estimated parameters was derived for the viscosity increase on the basis of apparent reaction kinetics. The model was used to control the viscosity and to predict the total reaction time of the resinate process. The kinetic data from the complex reaction media was obtained by acid value titration and by FTIR spectroscopic analyses using a conventional calibration method to measure the resinate concentration and the concentration of free rosin acids. A multivariate calibration method was successfully applied to make partial least square (PLS) models for monitoring acid value and solution viscosity in both mid-infrared (MIR) and near infrared (NIR) regions during the syntheses. The calibration models can be used for on line resinate process monitoring. In kinetic studies, two main reaction steps were observed during the syntheses. First a fast irreversible resination reaction occurs at 235 °C and then a slow thermal decarboxylation of rosin acids starts to take place at 265 °C. Rosin oil is formed during the decarboxylation reaction step causing significant mass loss as the rosin oil evaporates from the system while the viscosity increases to the target level. The mass balance of the syntheses was determined based on the resinate concentration increase during the decarboxylation reaction step. A mechanistic study of the decarboxylation reaction was based on the observation that resinate molecules are partly solvated by rosin acids during the syntheses. Different decarboxylation mechanisms were proposed for the free and solvating rosin acids. The deduced kinetic model supported the analytical data of the syntheses in a wide resinate concentration region, over a wide range of viscosity values and at different reaction temperatures. In addition, the application of the kinetic model to the modified resinate syntheses gave a good fit. A novel synthesis method with the addition of decarboxylated rosin (i.e. rosin oil) to the reaction mixture was introduced. The conversion of rosin acid to resinate was increased to the level necessary to obtain the target viscosity for the product at 235 °C. Due to a lower reaction temperature than in traditional fusion synthesis at 265 °C, thermal decarboxylation is avoided. As a consequence, the mass yield of the resinate syntheses can be increased from ca. 70% to almost 100% by recycling the added rosin oil.

Fotocatálise eletroquímica de atrazina sobre dióxido de titânio: efeito de diferentes parâmetros experimentais

The atrazine photoelectrochemical degradation has been examined in solutions containing TiO2 on immobilized films under a variety of experimental conditions. It was possible to observe that the supporting electrolyte nature affects the intensity of the photocurrent, being an indicative of the adsorption process. The disappearance of the organic molecule follows approximately a pseudo-first order kinetic. As mineralization product, NH4+ and NO3- ion have been identified. These results indicated that the formation of NH4+ ion can be associated to the effect of atrazine adsorption, due to need of potential adaptation together with a variation in the supporting electrolyte concentration.

Adaptação no método do peso da gota para determinação da tensão superficial: um método simplificado para a quantificação da CMC de surfactantes no ensino da química

The discussion based on surfactant cleaning action is commonly used in chemistry classrooms for the comprehension of theoretical concepts related to surface tension and micelle formation. The experimental quantification of surface tension of aqueous solutions of surfactants provides the practical instruments for this discussion. The present paper describes a simplification on the common apparatus employed for the drop-weight method, making the determination of surface tension accessible to any chemistry lab. The surface tension of various liquids and the critical micelle concentration, CMC, of three commercial surfactants were measured with this modified method, and proved to be consistent with literature values.

Determinação da concentração micelar crítica de ácidos húmicos por medidas de condutividade e espectroscopia

The aim of this study was the determination of the critical micelle concentration (CMC) of the sodium dodecyl sulfate (SDS) surfactant using spectroscopic and conductimetric determinations and to compare these methodologies in the determination of the CMC of different humic acids (HA). The CMC obtained by conductimetric determination was satisfactory. By spectroscopic determination two values of the CMC were obtained for HA. These values can be to due the intra and intermolecular interactions in the HA structure.

Azul de metileno imobilizado na celulose/TiO2 e SiO2/TiO2: propriedades eletroquímicas e planejamento fatorial

The electrochemical properties of methylene blue immobilized on cellulose/TiO2 and mixed oxide SiO2/TiO2 matrices were investigated by means of cyclic voltammetry. The electron mediator property of the methylene blue was optimized using a factorial design, consisting of four factors in two levels. The experimental observations and data analyses on the system indicate that the lowest peak separation occurs for Sil/TiOAM, 1.0 mol L-1 KCl solution and 20 mV s-1 scan rate, while values of current ratio closest to unity were found for Cel/TiOAM independent of electrolyte concentration, 0.2 or 1.0 mol L-1, and scan rate, 20 mV s-1 or 60 mV s-1.

Formação de micelas mistas entre o sal biliar colato de sódio e o surfactante aniônico dodecanoato de sódio

Mixed-micelle formation between sodium chlolate (NaC) and the anionic surfactant sodium dodecanoate (SDoD) in Tris-HCl buffer solutions, pH 9.00, varying the molar fraction of the surfactants, was investigated by means of electrical conductivity and steady-state fluorescence of pyrene. The critical micelar concentration (cmc) was measured from the equivalent conductance versus the square root of the molar surfactant concentration plots and the regular solution theory (RST) was used to predict the mixing behavior. The I1/I3 pyrene ratio-surfactant concentration plots were used as an additional technique to follow the behavior and the changes in the micropolarity of the mixed micelles.