O desenvolvimento de nanocarreadores a base de albumina são considerados biocompatíveis e biodegradáveis, e tem sido extensivamente estudada com objetivo de novas alternativas de tratamento para inúmeras doenças. A característica mais relevante reside no fato de que estes sistemas proteicos serem capazes de atravessar a barreira Hematoencefálica (BHE) e atingir as células-alvo, a partir de sinalizações por canais específicos na barreira cerebral. Por serem proteínas com ligações covalentes, pode-se afirmar que o processo de clivagem proteolítica tende a ser realizado pelas enzimas pertencente à família das proteases. Dada à importância desses sistemas de entrega de fármacos (DDS) e sua eficaz permeação através da BHE, propôs-se um desenvolvimento científico multidisciplinar combinando-se protocolos, técnicas e ensaios experimentais das áreas de tecnologia farmacêutica, nanotecnologia e química para realização da incorporação do fotoativo ou outros compostos, como a ftalocianina de cloro alumínio (AlClPc ou Pc) livre e/ou pré encapsuladas e as nanopartículas magnéticas, nestes sistemas de DDS conhecidos como nanopartícula de albumina (NpA). Dentre as técnicas usadas nestes estudos destaca-se tanto o método de cross-linking térmico (via Térmica) quanto o químico (via Química), sendo que no segundo, foram utilizados 2 reagentes distintos, o glutaraldeído e o gliceraldeído, os quais foram analisados e comparados neste projeto de pesquisa. Análises de Microscopia Eletrônica de Varredura (MEV), Microscopia de Força Atômica (MFA), medidas de estabilidade por ZetaSizer demonstraram claramente que as nanopartículas preparadas pelos diferentes reagentes possuíam formato esféricos, diâmetro médio em torno de 200 nm e eram homogêneas, entretanto, apenas os nanocarreadores preparados com GU apresentaram elevada repulsão eletrostática (prevenindo a agregação das mesmas). Após caracterização, os estudos foram baseados na utilização da AlClPc como fotoativo aplicado a terapia fotodinâmica (TFD) para o tratamento in vitro das doenças que acometem o sistema nervoso central (SNC). / The development of albumin-based nanocarriers, which are nontoxic and biocompatible and biodegradable, have been extensively studied for seeking new alternatives of the treatment for numerous diseases. The most relevant characteristic is that these protein-based systems could across the blood-brain barrier (BBB) and selectively achieve the target cells within of the brain. These nanocarriers are proteins-based and have covalent bonds, and consequently it can be digested by a class of enzymes belonging to the protease family, which rapidly degrade the protein-based nanoparticles through of the proteolytic cleavage process. Given the importance of these drug delivery systems (DDS) and their effective permeation through BBB, it was proposed a multidisciplinary scientific development combining protocols, techniques and experimental tests of the areas of pharmaceutical technology, nanotechnology and chemistry to carry out the incorporation of the photoactive or another compound, as aluminum chlorine phthalocyanine (AlClPc or Pc), free and/or pre-encapsulated or magnetic nanoparticles in these albumin-based DDS systems known as albumin nanoparticles (NpA). Among the techniques used in these studies we highlight by thermal cross-linking method (via Thermal) and chemistry (via Chemistry), in this second, it was used 2 reagents, glutaraldehyde and glyceraldehyde, that were analyzed and compared in this research project. From Scanning Electron Microscopy, Atomic Force Microcopy, Zeta potential measurements, we have clearly shown that the elaborated nanoparticles (NPs) have a smaller size with a spherical shape and are more homogeneous, however only the nanoparticles prepared with glutaraldehyde showed greater electronic repulsion (preventing their aggregation). After the characterization, the studies were based on the use of AlClPc as a photoactive applied in the photodynamic therapy (PDT) for the treatment of central nervous system (CNS) diseases.

No description available.

O objetivo do presente estudo foi o de avaliar a influência da associação dos tensoativos cetrimida 0,2%, cetrimida 0,1% e cloreto de benzalcônio 0,008% aos hipocloritos de sódio e de cálcio 2,5% nas propriedades de pH, quantidade de cloro livre, tensão superficial, ângulo de contato, dissolução pulpar e atividade antimicrobiana. O pH e a concentração de cloro ativo foram avaliados por pHmetro digital e pela titulação, respectivamente. A tensão superficial foi mensurada através da técnica do anel de platina com um tensiômetro de Du Noüy. O ângulo de contato das soluções em bases de dentina humana foi aferido pelo software Drop Shape Analyzer. Para a análise da dissolução pulpar foram utilizados fragmentos de polpas bovinas e os resultados foram expressos por percentual de perda de massa. A atividade antimicrobiana frente ao Enterococcus faecalis foi realizada pelo método de difusão em Ágar. Os resultados mostraram que a associação de tensoativos aos hipocloritos de sódio e cálcio não alterou as propriedades de pH, cloro livre e dissolução pulpar das soluções. O hipoclorito de cálcio apresentou o maior valor de tensão superficial (72,13 ± 1,82 mN/m). Quando associados aos tensoativos, os hipocloritos de sódio e cálcio tiveram uma redução significativa da tensão superficial. O mesmo foi observado para o ângulo de contato. Os tensoativos apresentam atividade antimicrobiana. A associação dos hipocloritos à cetrimida 0,2% ou 0,1% aumentou o halo de inibição frente ao Enterococcus faecalis. Concluiu-se que a associação de tensoativos não modificaram as propriedades de pH, cloro livre e dissolução pulpar dos hipocloritos de sódio e cálcio 2,5%. Porém, ela foi capaz de diminuir a tensão superficial e o ângulo de contato das soluções. Ainda, a associação da cetrimida 0,2% e 0,1% melhorou a capacidade antimicrobiana dos hipocloritos. / The aim of this study was to evaluate the influence of surfactants 0,2% or 0,1% cetrimide or 0,008% benzalkonium chloride on 2.5% sodium and calcium hypochlorite in the properties of pH, free chlorine content, surface tension, contact angle, pulp dissolution and antimicrobial activity. The pH and free chlorine content were evaluated by digital pHmeter and by titration, respectively. Surface tension was measured by the platinum ring technique with a Du Noüy tensiometer. Solution’s contact angle in human dentin surfaces was checked by Drop Shape Analyzer software. Bovine pulps were used for pulp dissolution analysis and the dissolving capacity was expressed by percentual weight loss. Antimicrobial activity over Enterococcus faecalis was evaluated through the ágar diffusion method. The surfactants association on sodium and calcium hypochlorites did not alter pH, free chlorine content and pulp dissolution properties. Calcium hypochlorite had the higher surface tension (72,13 ± 1,82 mN/m). However, when sodium and calcium hypochlorite were associated to surfactants, a significant reduction of surface tension occured. The same was observed for contact angle analysis. The surfactants used in this study have antimicrobial activity. The association of 0,2% or 0,1% cetrimide enhanced antimicrobial activity of both hypochlorites. It was possible to conclude that surfactants association did not alter pH, free chlorine content and pulp dissolution properties of 2,5% sodium and calcium hypochlorite. It was capable to reduce surface tension and contact angle of the solutions. Moreover, the 0,2% or 0,1% cetrimide association increased antimicrobial activity of hypochlorite.

Estudaram-se soluções para o pós-tratamento de efluentes de reatores UASB e de lagoas de estabilização visando à utilização em irrigação de culturas agrícolas. Nesta aplicação, normalmente são desejáveis bons níveis de remoção de sólidos em suspensão e graus elevados de desinfecção, além da conservação dos principais nutrientes. No caso do efluente de reatores UASB em escala real, foram construídas unidades em escala piloto envolvendo sedimentação, filtração e radiação UV. No primeiro experimento, o efluente dos reatores UASB passou por filtro de areia pressurizado em alta taxa e por reator UV de fluxo contínuo. Nesta etapa a concentração de sólidos em suspensão (SST) no efluente dos reatores UASB teve média de 233 mg/L, devido a problemas operacionais, sendo que o filtro apresentou eficiência média de 60% de remoção de sólidos em suspensão. Porém, como o filtrado apresentou absorbância ainda elevada, média de 0,476 cm-¹, a desinfecção UV resultou ineficiente e a contagem de coliformes do efluente final incompatível com o uso agronômico pretendido. No segundo experimento, o efluente dos reatores UASB recebeu tratamento complementar passando por decantador de alta taxa e filtração em leito de manta geotêxtil, seguindo finalmente para a desinfecção UV. A concentração de SST no efluente dos reatores UASB, sanados os problemas operacionais da ETE teve valor médio de 82 mg/L. Com essa concentração afluente relativamente baixa, o decantador lamelar demonstrou-se pouco eficiente e apresentou efluente com SST médio de 67 mg/L. No entanto, foi bastante útil para conter picos de concentração de sólidos no efluente dos reatores UASB, protegendo a etapa posterior de filtração. No efluente do filtro de manta geotêxtil, o SST médio foi de apenas 7 mg/L., ABS (254nm) de 0,245 cm-1 e Turbidez de 11 UNT. A desinfecção do efluente por radiação ultravioleta com dose recebida de 2,44 W.h/m³, resultou satisfatória com média geométrica de 1,12x101 NMP/100mL de E coli. No caso do efluente de sistema de lagoas de estabilização em escala real, aplicou-se pós-tratamento em escala piloto composto de filtro de areia pressurizado de alta taxa seguido de desinfecção por hipoclorito de sódio. A concentração de SST no efluente da lagoa facultativa teve média de 117 mg/L, enquanto que a média no efluente do filtro foi de 87 mg/L. Para concentrações de cloro dosado de 2,9; 6,2 e 11,7 mg/L, as médias geométricas das densidades de E coli no efluente final resultaram 1,13x10² NMP/100mL, 1,01x101 NMP/100mL e valor não detectado pelo método, respectivamente. Concluiu-se que é possível aplicar pós-tratamentos relativamente simples aos efluentes de reatores UASB e de lagoas de estabilização, quando se deseja uso agronômico e as principais condições operacionais destas unidades puderam ser avaliadas. / It was studied the application of a simple and economical post-treatment of effluent from wastewater treatment plant for the purpose of use on irrigation of agricultural crops. The research was conducted in two different wastewater treatment plants, (1) WTP UASB reactors with two application of post-treatment: (1.1) Post treatment with a sand bed filter pressurized at high-rate followed by ultraviolet disinfection. In this step, the concentration of suspended solids (TSS) in the effluent from the UASB reactor was 233 mg/L, the filter had efficiencies of 60% removal of suspended solids in the effluent from the UASB reactor, however, was not an appropriate result for effective disinfection of the effluent in the ultraviolet reactor. Absorbance values reached an average of 0.476 cm-¹. (1.2) Post-treatment at a high rate clarifier and on geotextile bed filtration to apply the ultraviolet disinfection. The concentration of TSS in the UASB reactor effluent has an average value of 82 mg/L, the concentration of the same parameter in the effluent from the clarifier was 67 mg/L and effluent of the filter geotextile, 7 mg/L. The system removed 91% of TSS in the effluent of the UASB reactor. In this experiment there was obtained a post-treated effluent with ABS (254nm) of 0.245 cm-1 and a turbidity of 11 NTU. The disinfection of the effluent by ultraviolet radiation with a dose received of 2.44 W.h/m³, obtained satisfactory results with geometric mean of 1.12x101 NMP/100mL E coli. (2) WTP by stabilization ponds with post-treatment in a pressurized sand filter followed by highrate disinfection by sodium hypochlorite solution. A TSS concentration in the effluent from facultative pond had an averaged 117 mg/L, the concentration of the same parameter in the effluent of the filter was 87 mg/L. With application of 2.88 mgCl2/L resulted in 1.13x10² NMP/100mL E coli, for the application of 6.2 and 11.7 mg/L chlorine was obtained 1.01x101 NMP/100mL E coli and ND, respectively.

Introdução: Organismos pertencentes ao gênero Aeromonas estão amplamente distribuídos no ambiente aquático sendo atualmente considerados como patógenos emergentes. Estudos demonstraram que, estes podem produzir uma série de fatores de virulência, e ainda um maior número de casos clínicos vêm sendo confirmados e atribuídos às diferentes espécies de Aeromonas. Objetivo: Estudar a ocorrência do gênero Aeromonas em efluentes de um sistema de lagoas de estabilização e discutir o significado da presença destes para a saúde pública. Métodos: A determinação de Aeromonas spp foi realizada pela técnica de tubos múltiplos (NMP/100 mL). Para a verificação da presença e ausência (PA) as colônias foram isoladas em ágar sangue ampicilina, ágar amido ampicilina e ágar MacConkey. As colônias que apresentaram resultados presuntivos para o grupo Aeromonas foram submetidas ao reisolamento em Ágar Amido, e a provas bioquímicas para identificação das espécies. O perfil plasmidial foi realizado de acordo com a metodologia descrita por BIRNBOIN & DOLLY 1979. Resultados: Aeromonas spp foram isoladas em 72,4% e 55,1% das amostras provenientes da entrada e saída da lagoa anaeróbia respectivamente, e em 48,3% da saída da lagoa facultativa variando as contagens entre <3 e 3,0x109 NMP/100mL. Na unidade de desinfecção por cloro entre <3 e 9,0 x 105 NMP/mL Conclusões: Observou-se que embora haja uma tendência de decaimento nas contagens de Aeromonas, não é possível eliminá-las do sistema estudado, mesmo após cloração. Esses organismos podem representar um risco à saúde devido à seleção de cepas resistentes que são lançadas no meio ambiente. / Introduction: Organisms of the genus Aeromonas are widely distributed in the aquatic environment, being now considered emerging organisms. Studies show that these organisms can produce a series of virulence factors, and that a major number of clinic cases have been confirmed and attributed to the different species of Aeromonas. Objective: Study the occurrence of the genus Aeromonas in effluents of a stabilization ponds system and discuss the meaning of the presence of these organisms for public health. Methods: Aeromonas spp determination was carried out by the most probable number technique (NMP/100mL). To verify the presence or absence, the colonies were isolated in ampicilin blood agar, starch agar, and Mc Conkey agar. Colonies showing presumptive results for Aeromonas group were re isolated in starch agar and to biochemical tests to identify the specie. The plasmidial profile was carried out according to the methodology described by BIRNBOIN & DOLLY 1979. Results: Aeromonas spp were isolated in 72,4% and 55.1% of the samples from the afluent and the end of anaerobic lagoons, respectively, in 48.3% of the effluent of the facultative lagoon in counts that varied from <3 and 3.0x109 NMP/100mL. In the disinfection unit counts varied from <3 and 9.0x105 NMP/100mL. Conclusions: It was possible to observe that even though a tendency of decaiment was noted for the counts of Aeromonas, it was not possible to totally eliminate this organisms from the studied system, even after the chlorination. These organisms could pose a health risk due to the selection of resistant strains released in the environment

Este trabalho teve por objetivo estudar a desinfecção seqüencial cloro-radiação ultravioleta e ozônio-radiação ultravioleta a fim de avaliar a resistência de microrganismos indicadores de poluição fecal - E. coli, coliformes totais e Clostridium perfringens - e compará-la à dos protozoários patogênicos: Giardia spp. e Cryptosporidium spp.. Houve, primeiramente, monitoramento do reator anaeróbio UASB cujo efluente foi utilizado neste estudo. Foi, então, verificado o comportamento das espécies residuais de cloro no esgoto e conduzido um estudo de parâmetros indicadores (pH, potencial de oxi-redução e condutividade) para o breakpoint. Na desinfecção, foram empregados o cloro, ozônio e radiação ultravioleta; separados, e seqüencialmente. Os ensaios realizados com ozônio promoveram remoção de DQO, sólidos e dos valores de absorbância em 254 nm, diferentemente do cloro. A ordem crescente de resistência à desinfecção foi: E. coli < coliformes totais < C. perfringens < protozoários. Houve correlação em alguns ensaios entre a bactéria esporulada C. perfringens e Giardia spp.. O efeito sinérgico, promovido pela desinfecção seqüencial, foi evidenciado em alguns experimentos para C. perfringens e Giardia spp. / The present dissertation reports on the study of the sequential disinfection with chlorine-ultraviolet radiation and ozone-ultraviolet radiation to evaluate the resistance of microorganisms that indicate fecal pollution - E. coli, total coliforms and Clostridium perfringens - and compare it to the resistance of pathogenic protozoa: Giardia spp. and Cryptosporidium spp.. Firstly, the UASB reactor, whose effluent was utilized in this study, was monitored. Then the behavior of the residual species of chlorine in the sanitary sewage was verified and a study of the indicating parameters (pH, oxi-reduction potential and conductivity) for the breakpoint was conducted. Chlorine, ozone and ultraviolet radiation were used separately and sequentially in the disinfection. Tests performed with ozone promoted removal of COD, solids and absorbance values of 254 nm, differently from chlorine. The order of resistance to disinfection was: E. coli < total coliforms < Clostridium perfringens < protozoa. There was a correlation in some tests between spore-forming bacterium Clostridium perfringens and Giardia spp.. The synergic effect caused by the sequential disinfection was observed in some experiments for C. perfringens and Giardia spp.

Two long-lived halogen radionuclides (36Cl, T1/2 = 301 kyr, and 129I, T1/2 = 15.7 Myr) have been studied by means of Accelerator Mass Spectrometry (AMS) at the Uppsala Tandem Laboratory. The 36Cl measurements in natural samples using a medium-sized tandem accelerator (~1 MeV/amu) have been considered. A gas-filled magnetic spectrometer (GFM) was proposed for the separation of 36Cl from its isobar, 36S. Semi-empirical Monte-Carlo ion optical calculations were conducted to define optimal conditions for separating 36Cl and 36S. A 180° GFM was constructed and installed at the dedicated AMS beam line. 129I has been measured in waters from the Arctic and North Atlantic Oceans. Most of the 129I currently present in the Earth's surface environment can be traced back to liquid and gaseous releases from the nuclear reprocessing facilities at Sellafield (UK) and La Hague (France). The anthropogenic 129I inventory in the central Arctic Ocean was found to increase proportionally to the integrated 129I releases from these reprocessing facilities. The interaction and origin of water masses in the region have been clearly distinguished with the help of 129I labeling. Predictions based on a compartment model calculation showed that the Atlantic Ocean and deep Arctic Ocean are the major sinks for the reprocessed 129I. The variability in 129I concentration measured in seawater along a transect from the Baltic Sea to the North Atlantic suggests strong enrichment in the Skagerrak–Kattegat basin. The 129I inventory in the Baltic and Bothnian Seas is equal to ~0.3% of the total liquid releases from the reprocessing facilities. A lake sediment core sampled in northeastern Ireland was analyzed for 129I to study the history of the Sellafield releases, in particular the nuclear accident of 1957. High 129I concentration was observed corresponding to 1990 and later, while no indication of the accident was found. The results of this thesis research clearly demonstrate the uniqueness and future potential of 129I as a tracer of processes in both marine and continental archives.

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are by-products emitted from combustion sources such as municipal solid waste (MSW) incineration plants. These organic compounds are recognized as toxic, bioaccumulative and persistent in the environment. PCDD/Fs are removed from flue gases before released from MSW incineration. However, the PCDD/Fs are not destroyed but retained in the residues, thus in the environment. Understanding the pathways that lead to their formation is important in order to develop ways to suppress their formation and prevent their release into the environment. Suppressing the formation can also allow less expensive air pollution control system to be used, and/or the costs of thermally treating the residues to be reduced. The main objective of the studies underlying this thesis was to elucidate process, combustion and fuel parameters that substantially affect the emission levels and formation of PCDD/Fs in flue gases from MSW incineration. The experiments were conducted under controllable, realistic combustion conditions using a laboratory-scale reactor combusting artificial MSW. The parameter found to most strongly reduce the PCDD/F emissions, was prolonging the flue gas residence time at a relatively high temperature (460°C). Increasing the sulfur dioxide (SO2) to hydrogen chloride (HCl) ratio to 1.6 in the flue gas was also found to reduce the PCDF levels, but not the PCDD levels. Fluctuations in the combustion process (carbon monoxide peaks), high chlorine levels in the waste (1.7%) and low temperatures in the secondary combustion zone (660°C) all tended to increase the emission levels. The PCDD/PCDF ratio in the flue gas was found to depend on the chlorine level in the waste, fluctuations in the combustion process and the SO2:HCl ratio in the flue gas. The formation pathways were found to be affected by the quench time profiles in the post-combustion zone, fluctuations in the combustion process and addition of sulfur. In addition, increased levels of chlorine in the waste increased the chlorination degrees of both PCDDs and PCDFs. A tendency for increased SO2 levels in the flue gas to increase levels of polychlorinated dibenzothiophenes (sulfur analogues of PCDFs) was also detected, however the increases were much less significant than the reduction in PCDF levels.

Chlorine solid-state nuclear magnetic resonance (SSNMR) is an ideal site specific probe of chloride-containing solids as SSNMR tensor properties are sensitive to the local chlorine environment. In this thesis, the development and use of chlorine SSNMR as a method to characterize a wide variety of chemical environments was explored. Ultrahigh field, and multi-field studies were essential to overcome the difficulties associated with the collection of chlorine SSNMR spectra. Benchmark chemical shift (CS) and electric field gradient (EFG) tensor data were collected for organic chloride systems, including several amino acid hydrochlorides. These experiments demonstrated the sensitivity of chlorine SSNMR to slight changes in chemical environment. Quantum chemical calculations were used to complement experimental data, with the gauge-including projector augmented wave DFT (GIPAW-DFT) method shown to yield better agreement than B3LYP or RHF methods. The GIPAW-DFT method was found to slightly, but systematically, overestimate the chlorine quadrupolar coupling constant and the CS tensor span. Other organic chlorides examined by chlorine SSMR included a known ion receptor, meso-octamethylcalix[4]pyrrole. This compound was found to have a very small quadrupole interaction (QI), but significant chemical shift anisotropy (CSA). GIPAW-DFT calculations were also utilized and, in combination with the experimental results, used to identify the solvate structure of the material analyzed by NMR. Chlorine SSNMR was further used to study different solvate structures and polymorphism. The technique was an effective means to distinguish different room temperature polymorphs of benzidine hydrochloride, despite the similarities of the chloride environments. In the case of magnesium chloride, chlorine SSNMR was sensitive to the level of hydration and through the use of GIPAW-DFT calculations, the identity of an unknown hydrate was determined. An analysis of several group thirteen chlorides demonstrated that chlorine SSNMR was also capable of characterizing the chlorine environment in cases where the QI is large, despite the resulting broad line widths. In these systems GIPAW-DFT calculations also yielded excellent agreement with experimental values. Throughout this research, chlorine SSNMR has been shown to be a useful and effective means to study both organic and inorganic chlorides, with computational methods proving to be an important complement to experimental data.

This dissertation attempts to extend the classes of halogen-containing systems which may be studied using solid-state nuclear magnetic resonance (SSNMR). As line shape broadening due to the quadrupolar interaction (QI) scales inversely with the applied field, high-field magnet technology is indispensable for this research. Combining advanced radiofrequency pulse sequences with high-field wideline data acquisition allowed for the collection of very broad SSNMR signals of all quadrupolar halogen nuclei (i.e., 35/37Cl, 79/81Br and 127I) within a reasonable amount of experimental time. The initial systems for study were of the MX2 variety (M = Mg, Ca, Sr, Ba; X = Cl, Br, I). In total, 9 anhydrous compounds were tested. The effects of hydrate formation were tested on 7 additional compounds. Systematic trends in the observed δiso values (and to a lesser extent, Ω and CQ) were found to be diagnostic of the extent of hydration in these materials. Resolving power was successfully tested using SrBr2, which possesses 4 magnetically unique sites. The composition of CaBr2•xH2O was convincingly determined using SSNMR data and the hydration trends noted above. The sensitivity of the QI to the local bonding environment (e.g., bond distance changes of less than 0.05 Å) was used to refine (when coupled with gauge-including projector augmented-wave density functional theory (GIPAW DFT) quantum chemical computations) the structure of MgBr2, and was used to correct prior NMR data for CaCl2 (earlier accounts had been performed upon a CaCl2 hydrate). During NMR data analysis of certain iodine-containing materials, it was found that standard fitting software (which uses perturbation theory) could not reproduce the observations. Proper analysis required the use of exact simulation software and allowed for the observation of high-order quadrupole-induced effects (HOQIE). This motivated further studies using rhenium-185/187 nuclei, where it was expected that HOQIE would be more dramatic. The observed rhenium SSNMR spectra possessed additional fine structure that had never been observed before experimentally, nor would be expected from currently-available perturbation theory analysis software. Lastly, preliminary results are shown where 127I SSNMR is used to study important supramolecular systems, and the composition of the popular synthetic reagent ‘GaI’ is elucidated.