Protecting the quality and quantity of our water resources requires advanced treatment technologies capable of removing nutrients from wastewater. This research work investigated the capability of one such technology, a hollow-fiber membrane-aerated biofilm reactor (HFMBR), to achieve completely autotrophic nitrogen removal from a wastewater with high nitrogen content. Because the extent of oxygenation is a key parameter for controlling the metabolic processes that occur in a wastewater treatment system, the first part of the research investigated oxygen transfer characteristics of the HFMBR in clean water conditions and with actively growing biofilm. A mechanistic model for oxygen concentration and flux as a function of length along the non-porous membrane fibers that comprise the HFMBR was developed based on material properties and physical dimensions. This model reflects the diffusion mechanism of non-porous membranes; namely that oxygen follows a sorption-dissolution-diffusion mechanism. This is in contrast to microporous membranes in which oxygen is in the gas phase in the fiber pores up to the membrane surface, resulting in higher biofilm pore liquid dissolved oxygen concentrations. Compared to offgas oxygen analysis from the HFMBR while in operation with biofilm growing, the model overpredicted mass transfer by a factor of approximately 1.3. This was in contrast to empirical mass transfer coefficient-based methods, which were determined using either bulk aqueous phase dissolved oxygen (DO) concentration or the DO concentration at the membrane-liquid interface, measured with oxygen microsensors. The mass transfer coefficient determined with the DO measured at the interface was the best predictor of actual oxygen transfer under biofilm conditions, while the bulk liquid coefficient underpredicted by a factor of 3. The mechanistic model exhibited sensitivity to parameters such as the initial lumen oxygen concentration (at the entry to the fiber) and the diffusion coefficient and partitioning coefficients of oxygen in the silicone membrane material. The mechanistic model has several advantages over empirical-based methods. Namely, it does not require experimental determination of KL, it is relatively simple to solve without the use of advanced mathematical software, and it is based upon selection of the membrane-biofilm interfacial DO concentration. The last of these is of particular importance when designing and operating HFMBR systems with redox (aerobic/anoxic/anaerobic) stratification, because the DO concentration will determine the nature of the microenvironments, the microorganisms present, and the metabolisms that occur. During the second phase of the research, the coupling of two autotrophic metabolisms, partial nitrification to nitrite (nitritation) and anaerobic ammonium oxidation, was demonstrated in a single HFMBR. The system successfully treated a high-strength nitrogen wastewater intended to mimic a urine stream from such sources as extended space missions. For the last 250 days of operation, operating with an average oxygen to ammonia flux (J_O₂/J_NH₄⁺) of 3.0 resulted in an average nitrogen removal of 74%, with no external organic carbon added. Control of nitrite-oxidizing bacteria (NOB) presented a challenge that was addressed by maintaining the J_O₂/J_NH₄⁺ below the stoichiometric threshold for complete nitrification to nitrate (4.57 g O₂ / g NH₄⁺). The DO-limiting condition resulted in formation of harmful gaseous emissions of nitrogen oxides (NO, N2O), which could not be prevented by short-term control strategies. Controlling JO2/JNH4+ prevented NOB proliferation long enough to allow an anaerobic ammoniaoxidizing bacteria (AnaerAOB) population to develop and be retained for >250 days. Addition of a supplemental nutrient solution may have contributed to the growth of AnaerAOB by overcoming a possible micronutrient deficiency. Disappearance of the gaseous nitrogen oxide emissions coincided with the onset of anaerobic ammonium oxidation, demonstrating a benefit of coupling these two autotrophic metabolisms in one reactor. Obvious differences in biofilm density were evident across the biofilm depth, with a region of low density in the middle of the biofilm, suggesting that low cell density or exocellular polymeric substances were primarily present in this region, Microbial community analysis using fluorescence in situ hybridization (FISH) did not reveal consistent trends with respect to length along the fibers, but radial stratification of aerobic ammonia-oxidizing bacteria (AerAOB), NOB, and AnaerAOB were visible in biofilm section samples. AerAOB were largely found in the first 25% of the biofilm near the membrane, AnaerAOB were found in the outer 30%, and NOB were found most often in the mid-depth region of the biofilm. This community structure demonstrates the importance of oxygen availability as a determinant of how microbial groups spatially distribute within an HFMBR biofilm. The combination of these two aspects of the research, predictive oxygen transfer capability and the effect of oxygen control on performance and populations, provides a foundation for future application of HFMBR technology to a broad range of wastewaters and treatment scenarios. / Ph. D.

Mathematical models of a nitritation: anaerobic ammonia oxidation (anammox)-coupled biofilm in a counter-diffusion hollow fiber membrane bioreactor (HFMBR) and a nitritation: anammox-coupled biofilm in a co-diffusion rotating biological contactor (RBC) were developed and implemented using AQUASIM. Four different start-up scenarios on the nitritation: anammox-coupled biofilm in an HFMBR were investigated. The supply of oxygen was simulated with the flow through the lumen of the hollow fiber membrane. For the four scenarios, two scenarios investigated the start-up when nitrite was supplied in the feed while the other two scenarios investigated when the source of nitrite was through nitritation only. The results showed that the presence of nitrite in the feed facilitated the start-up of the reactor. In addition, the results also showed that increasing oxygen flux through the membrane up to a certain ratio of ammonia flux with oxygen flux affected reactor performance by improving nitrogen removal and reducing start up time. For the nitritation: anammox-coupled biofilm in an RBC, four different process options were investigated: the number of reactors, the initial anammox (AnAOB) biomass fraction, the bulk oxygen concentration and the maximum biofilm thickness. Modeling results revealed that the steady state total nitrogen removal in RBC reactors in series occurred primarily in the first and second reactors. It is concluded that the number of reactors in series dictates the effluent performance and, therefore, this number can be selected depending upon the desired total nitrogen removal. Simulation results also revealed that increasing the initial AnAOB biomass fraction from 0.01% to 1.0% had no effect in the steady state nitrogen removal but had an effect in the required time to reach the steady state total nitrogen removal and the maximum biofilm thickness. Modeling results of the third process option showed that increasing the bulk oxygen concentration in the reactor from 0.2 g/m3 to 5 g/m3 linearly increased the steady state total nitrogen removal and reduced the time to reach the maximum biofilm thickness. Beyond 5 g/m3, steady state total nitrogen removal decreased. In addition, simulation results revealed that the thicker biofilm clearly showed a more linear correlation between the increase in bulk oxygen concentration and the increase in the steady state total nitrogen removal within a range of bulk oxygen concentrations. The results showed that RBC performance could be controlled by several process options: the number of reactors in series, initial biomass fraction, the bulk oxygen concentration and the maximum biofilm thickness. The mathematical modeling results for the HFMBR and RBC have shown that both have potential as carriers for nitritation: anammox-coupled biofilms targeted at the removal of nitrogen in the wastewater. / Master of Science

In recent years, membrane gas absorption technology has been considered as one of the promising alternatives to conventional techniques for CO2 capture due to its favorable mass transfer performance. As a hybrid approach of chemical absorption and membrane separation, it exhibits a number of advantages, such as operational flexibility, compact structure, high surface-area-to-volume ratio, linear scale up, modularity and predictable performance. One of the main challenges of membrane gas absorption technology is the membrane wetting by absorbent over prolonged operating time, which may significantly decrease the mass transfer coefficients of the membrane module. In this thesis, the experimental was set up to investigate the dependency of CO2 removal efficiency and mass transfer rate on various operating parameters, such as the gas and liquid flow rates, absorbent type and concentration and volume fraction CO2 at the feed gas inlet. In addition, the simultaneous removal of SO2 and CO2 was investigated to evaluate the feasibility of simultaneous desulphurization and decarbonization in the same membrane contactor. During 14 days of continuous operation, it was observed that the CO2 mass transfer rate decreased significantly following the operating time, which was attributed to partial membrane wetting. To better understand the wetting mechanism of membrane pores during their prolonged contact with absorbents, immersion experiments for up to 90 days were carried out. Various membrane characterization methods were used to illustrate the wetting process before and after the membrane fibers were exposed to the absorbents. The characterization results showed that the absorbent molecules diffused into the polypropylene polymer during the contact with the membrane, resulting in the swelling of the membrane. In addition, the effects of operating parameters such as immersion time and absorbent type on the membrane wetting were investigated in detail. Finally, based on the analysis results, methods to smooth the membrane wetting were discussed. It was suggested that improving the hydrophobicity of polypropylene membrane by surface modification may be an effective way to improve the long-term operating performance of membrane contactors. Therefore, the polypropylene hollow fibers were modified by depositing a thin superhydrophobic coating on the membrane surface to improve their hydrophobicity. The mixture of cyclohexanone and methylethyl ketone was considered as the best non-solvent to achieve the fiber surface with good homogeneity and acceptably high hydrophobicity. In the long-period operation, the modified membrane contactor exhibited more stable and efficient performance than the untreated one. Hence, surface treatment provides a feasibility of improving the system stability for CO2 capture from the view of long-term operation. / En av de tekniker som under senare framhållits som ett lovande alternativ till konventionell CO2-avskiljning är membran-gas-absorptionstekniken på grund av god prestanda vad gäller masstransport. Det blandade angreppssättet med både kemisk absorption och membranseparation har en rad fördelar, såsom driftflexibilitet, kompakt konstruktion, högt yt-volymsförhållande, linjär uppskalning, modularitet och förutsägbar prestanda. En av de viktigaste utmaningarna för membran-gas-absorptionstekniken är vätningen av membranet med absorbenten under långa drifttider, vilket väsentligt kan minska membranmodulens masstransportkoefficienter.  I avhandlingen har en rad olika driftparametrars påverkan på CO2-reningsgraden och massöverföringshastigheten undersökts. Driftparametrar inkluderar gas- och vätskeflöden, typ av absorbent och koncentration och volymfraktion av CO2 vid gasinloppet. Avskiljning av SO2 och CO2 har dessutom undersökts för att utvärdera möjligheten att samtidigt, i samma membranenhet, avlägsna svavel och kol. Under 14 dagars kontinuerlig drift konstaterades det att massöverföringshastigheten för CO2 minskade avsevärt med drifttiden, vilket hänfördes till partiell vätning av membranet.   För att bättre förstå mekanismerna för vätning av membranporer under långvarig kontakt med absorbenter genomfördes doppningsexperiment i upp till 90 dagar. Olika metoder för karakterisering av membran användes för att illustrera vätningsprocessen före och efter det att membranfibrerna exponerades för absorbenterna. Resultaten av karakteriseringen visade att absorbentmolekylerna spreds in i polypropenpolymeren under kontakten med membranet, vilket ledde till att membranet svällde. Dessutom undersöktes effekterna av driftsparametrar såsom nedsänkningstid och typ av absorbent i detalj. Slutligen, på grundval av analysresultaten, diskuterades metoder för att underlätta vätningen av membran. Att förbättra polypropylenmembranets hydrofobicitet genom modifiering av ytan föreslogs kunna vara ett effektivt sätt att förbättra den långsiktiga driftprestandan för membranenheter. Därför modifierades de ihåliga fibrerna av polyproylen med ett tunt lager av en superhydrofob beläggning på membranets yta för att förbättra hydrofobiciteten. En blandning av cyklohexanon och metyletylketon ansågs vara det bästa icke-lösningsmedlet för att få en fiber yta med god homogenitet och acceptabelt hög hydrofobicitet. Under lång driftperiod, uppvisade den modifierade membranenheten stabilare och effektivare prestanda än den obehandlade. Därför erbjuder ytbehandling en möjlighet till att förbättra systemets stabilitet för CO2-avskiljning när det gäller långsiktig drift. / VR-SIDA Swedish Research Links Programme

A lamotrigina (LTG) é um fármaco pertencente à classe das feniltriazinas utilizado no tratamento de crises epilépticas generalizadas e focais e no tratamento adjunto da epilepsia refratária. Devido à alta variabilidade interindividual, às interações medicamentosas e aos efeitos adversos apresentados durante a administração da LTG, a monitorização terapêutica nos pacientes que fazem uso deste fármaco é necessária para ajuste de dose individual e evitar os efeitos adversos. Assim, o objetivo deste trabalho foi a avaliação de duas técnicas de microextração: a microextração em fase líquida com fibras ocas (HF-LPME) e a microextração líquido-líquido dispersiva (DLLME) para análise da lamotrigina em amostras de plasma de pacientes epilépticos. Primeiramente foram definidas as condições eletroforéticas: foi utilizado um capilar de sílica fundida de 75 ?m de diâmetro interno e 50 cm de comprimento efetivo. O eletrólito de corrida (BGE) foi composto por ácido 2-morfolinoetanosulfônico (MES), na concentração de 130 mmol L-1 e pH 5,0. As análises foram realizadas à temperatura de 20°C e tensão de 15 kV. A amostra foi injetada hidrodinamicamente (0,5 psi por 10 s) e a detecção foi feita em 214 nm. Nestas condições a LTG e o padrão interno (PI), lidocaína, puderam ser analisados em menos de 7 minutos. A HF-LPME foi avaliada no modo de 3 fases, usando 500 ?L de plasma e 3,5 mL de solução fosfato de sódio 50 mmol L-1 pH 9,0 como fase doadora. O solvente utilizado para impregnar a fibra foi o 1-octanol. Como fase aceptora foram utilizados 60 ?L de solução de ácido clorídrico pH 4,0. Para avaliação da DLLME, foi necessária uma etapa de pré-tratamento da amostra (500 ?L de plasma) com 1 mL de acetonitrila. Após isto, 1,3 mL do sobrenadante foram adicionados a 4 mL de solução fosfato de sódio 50 mmol L-1 pH 9,0 e 120 ?L de clorofórmio (solvente extrator) foram injetados nesta amostra aquosa e 165 ?L de fase sedimentada foram recuperados. As características de desempenho analítico para ambos os métodos foram avaliadas, sendo obtida linearidade na faixa de concentração plasmática de 1-20 ?g/mL e limite inferior de quantificação (LIQ) de 1 ?g mL-1. Os ensaios de precisão e exatidão apresentaram valores de acordo com os guias oficiais. Além disso, os métodos foram seletivos, não apresentaram efeito residual e as amostras foram estáveis. Os valores de recuperação foram de 54,3 e 23% para HF-LPME e DLLME, respectivamente. Os métodos validados foram aplicados com sucesso em amostras de plasma de pacientes epilépticos em tratamento com a LTG. Além disso, as duas técnicas foram comparadas e a HF-LPME apresentou vantagens em relação à DLLME, mostrando ser uma técnica promissora para análise de matrizes complexas, com reduzido consumo de solvente orgânico e possibilidade de automação. / Lamotrigine (LTG) is an antiepileptic drug, which belongs to the class of phenyltriazine that can be used in the treatment of new-onset and refractory epilepsy. Due to its high interindividual variability, drug interactions and the adverse effects presented during the LTG administration, therapeutic drug monitoring is very important to dose adjustment and to avoid toxicity effects. Thus, the goal of this study was to develop and validate two microextraction techniques: the hollow fiber liquid-phase microextraction (HF-LPME) and the dispersive liquid-liquid microextraction (DLLME) to analyze LTG in plasma samples of epileptic patients. First of all, the eletroforetic conditions were optimized. A fused-silica uncoated capillary with 75 ?m internal diameter, and 50 cm effective length was used. The 2-(N-morpholino)ethanesulfonic acid (MES) 130 mmol L-1 pH 5.0 was chosen as background electrolyte (BGE). The temperature and the voltage were kept constant at 20°C and 15 kV respectively. For sample injection, hydrodynamic injection mode was used, with a pressure of 0.5 psi applied for 10 s. The wavelength was set at 214 nm. Under final conditions, LTG and the internal standard (IS) lidocaine were analyzed in less than 7 minutes. HF-LPME was evaluated in the three phase mode. The analyte was extracted from 4.0 mL of a basic donor phase (composed of 500 ?L of plasma and 3.5 mL of sodium phosphate solution 50 mmol L-1 pH 9.0) into an organic phase composed of 1-octanol immobilized in the pores of the hollow fiber, and further into an acidic acceptor phase (hydrochloric acid solution pH 4.0) placed in the lumen of the fiber. To evaluate DLLME, the plasma samples were pretreated to remove the proteins, and 500 ?L of plasma sample was mixed with 1 mL of acetonitrile. After that, 1,3 mL of the upper layer was added to 4 mL of sodium phosphate solution 50 mmol L-1 pH 9.0, and 120 ?L of chloroform (extracting solvent) was rapidly injected in the aqueous sample and 165 ?L of the sedimented phase was collected. Under the optimized conditions, both methods were linear over the plasmatic concentration range of 1.0-20.0 ?g mL-1 and the lower limit of quantification (LLOQ) was 1.0 ?g mL-1. Both methods showed good precision, accuracy, selectivity to LTG, with no carryover and the samples were stable under the studied conditions. The recovery were 54,3 and 23% to HF-LPME and DLLME respectively. The validated methods were successfully applied for the quantification of LTG in plasma samples of epileptic patients. The techniques were compared and HF-LPME was more advantageous for being more suitable to analysis of complex matrices using small amount of organic solvent, and also can be automated.

Este trabajo ha estado dirigido al estudio de un proceso eficaz de separación que posibilite la recuperación de zinc de efluentes de decapado ácido de elevada toxicidad, así como su posterior concentración en una fase de características físico-químicas adecuadas para posibilitar su reciclado en baños electrolíticos. Para ello se propone la extracción líquido-líquido no dispersiva como tecnología limpia de elevada eficacia y con bajo requerimiento energético.Tras una exhaustiva revisión bibliográfica, se seleccionan el fosfato de tributilo y el agua de red como agentes extractante y reextractante respectivamente. A lo largo del trabajo y tras una etapa previa dirigida a la evaluación de la viabilidad técnica del proceso, se caracterizaron experimentalmente las reacciones responsables de las etapas de extracción y reextracción, así como la cinética del proceso de separación, para a continuación plantear el modelo matemático y determinar los parámetros característicos del sistema necesarios para el diseño y optimización del proceso de separación-concentración de zinc de efluentes de decapado ácido metálico. / The work was focused on the study of the recovery of zinc from spent pickling effluents, under conditions that permitted the recovery of electrolytic grade metal, thus, reducing the effluent toxicity and with valorisation, at the same time, of the component of higher added value. After a deep literature review, non dispersive solvent extraction using tributyl phosphate (TBP) and service water as extraction and back extraction agents, respectively, was selected as the best separatión alternative. The work started with the analysis of the process viability and included an experimental design of the equilibrium, and kinetics of the phenomena involved in the metal valorisation. The kinetic analysis of the membrane assisted process of zinc recovery from spent pickling effluents was carried out, obtaining the mathematical model and parameters needed for design and optimisation of the metal separation step in a valorisation process.

In this thesis, several types of scaffolds composed of different materials and designed structures and functions were fabricated by 3D plotting under mild conditions (room temperature and without using any organic solvent). Broad biomaterials including inorganic (such as calcium phosphate cement and mesoporous bioglass), organic (such as alginate and gelatin) and composite materials were prepared into printable pastes to plot as 3D scaffolds for bone tissue engineering. Organic/inorganic biphasic and bipartite structure, core/shell alginate/nano-hydroxyapatite and hollow fiber structure were designed and realized. Scaffolds with multi functions including suitable mechanical properties, sustained drug/protein delivery and in vitro vascularization were achievable. 3D plotting provided great achievements in the field of tissue engineering by preparing advanced scaffolds, as well as by plotting cell/matrix constructs, and even complex tissues and organs.

The drug abuse has created several problems, moral, social and economical, and does not have borders of social class, educational and religious. The chemicaltoxicological analysis is an indispensable resource to confirm the exposure of humans to these drugs. Depending on the purpose of analysis, various biological matrices can be used. Nowadays, hair is being recognized as a third fundamental biological sample for drug testing besides urine and blood. The collection of hair samples is simple, noninvasive being difficult its adulteration. The techniques based on the miniaturization of extraction have gained an important role on the world stage in relation to conventional techniques. Among these techniques, stand out to solid phase microextraction (SPME) and liquid phase microextraction (LPME). In this work, a analytical method was developed for determination of 9- tetrahydrocannabinol (9-THC), cannabidiol (CBD) and cannabinol (CBN) in human hair by headspace solid-phase microextraction (SPME) and hollow fiber liquid-phase microextraction (HF-LPME) using gas chromatography coupled to mass spectrometry, operating in tandem mode (GC-MS/MS). Initially, in step sample preparation, a small mass of hair (10 mg) was decontaminated with petroleum ether (2 mL) for 10 minutes of ultrasound application (3 times) followed by alkaline digestion (NaOH 1 M). A univariate design was used for the determination the better condictions of the parameters of HS-SPME: pH (10), temperature (90 °C), mass of hair (10 mg), extraction time (40 min), desorption time (10 min), ionic strength (Na2CO3), saturation time (10 min) and fiber (PDMS). For HF-LPME a fractional factorial design was used in the screening of some variables of this technique followed by central composite design in the evaluation of optimal values of variables. The variables assessed and the optimum values of these were: extraction solvent (butyl acetate), donor phase pH (14), agitation speed (600 rpm), extraction time (20 min), ionic strength (6.8 % m/v) and acceptor phase volume (20 μL). The methods were submitted to the validation process showed good linearity with coefficient of determination (R2) above 0.994. Precision was determined using two different concentrations (upper and lower limits of the linear range) and RSD values were between 6.6 and 16.4 % for HS-SPME and 4.4-13.7% for HF-LPME. Absolute recoveries were in the range 1.1 to 8.7 % (HS-SPME) and 4.4 to 8.9 % (HF-LPME). The limits of detection and quantification ranged between 7-62 pg mg-1 and from 0.0005-0.020 ng mg-1 to HS-LPME and HF-LPME, respectively. The 9-THC showed values of limits of quantification for both methods below the cut-off (LQ ≤ 100 pg mg-1). Finally, the methods developed and validated were applied in determining CBD, 9-THC and CBN in hair samples of patients from a center of rehabilitation for drug addicts. The concentrations were in the range of LD-0.018 ng mg-1 for CBD, LD-232 pg mg-1 for 9-THC and 9-300 pg mg-1 for CBN show the applicability of the method in monitoring studies. The concentration of cannabinoids in the samples ranged from limit of detection to 18 pg mg-1 for CBD, limit of detection to 232 pg mg -1 for 9-THC and 9 to 300 pg mg-1 to CBN demonstrate the applicability of the method in monitoring studies. / O consumo de drogas de abuso tem criado diversos problemas de ordem moral, social e econômica, além de não possuir fronteiras de classes sociais, educacionais e religiosas. A análise químico-toxicológica é um recurso indispensável para confirmar a exposição de pessoas a essas drogas. Dependendo da finalidade da análise, diversas matrizes biológicas podem ser utilizadas. Atualmente, o cabelo é reconhecido como uma das principais amostras biológicas para determinação de drogas, ao lado da urina e do sangue. A coleta de amostras de cabelo é um processo simples, não invasivo, sendo difícil sua adulteração. As técnicas baseadas na minituarização de extração têm ganhado um papel importante no cenário mundial frente às técnicas convencionais. Entre essas técnicas destacam-se a microextração em fase sólida (SPME) e a microextração em fase líquida (LPME). No presente trabalho, um método analítico foi desenvolvido para determinação de 9-tetraidrocanabinol (9- THC), canabidiol (CBD) e canabinol (CBN) em cabelo humano por microextração em fase sólida no modo headspace (HS-SPME) e microextração em fase líquida por fibra oca (HF-LPME) por cromatografia em fase gasosa e espectrometria de massas operando no modo tandem (GC-MS/MS). Na etapa de preparação da amostra, uma pequena massa de cabelo (10 mg) foi descontaminada com éter de petróleo (2 mL) por 10 minutos em ultra-som (3X), seguida de digestão alcalina (NaOH 1 mol L-1). Um planejamento univariado foi utilizado para o estudo das condições ótimas dos parâmetros de HS-SPME, tendo sido deferidos: pH (10), temperatura (90 ºC); massa de cabelo (10 mg); tempo de extração (40 min); tempo de dessorção (10 min); força iônica (Na2CO3); tempo de saturação (10 min) e fibra (PDMS). Para HF-LPME um planejamento fatorial fracionário foi empregado na triagem de algumas variáveis desta técnica seguido pelo planejamento composto central na avaliação dos valores ótimos das variáveis escolhidas: solvente de extração (acetato de butila), pH da fase doadora (14), velocidade de agitação (600 rpm), tempo de extração (20 min), força iônica (6,8 % m/v) e volume da fase aceptora (20 μL). Os métodos foram submetidos ao processo de validação demonstrando boa linearidade, com coeficientes de determinação (R2) acima de 0,994. A precisão foi determinada a partir dos limites inferior e superior da faixa linear apresentando valores de RSD entre 6,6 e 16,4% para HS-SPME e 4,4-13,7 % para HF-LPME. Recuperações absolutas foram de 1,1 a 8,7 % (HS-SPME) e 4,4 a 8,9 % (HF-LPME). Os limites de detecção (LD) e quantificação (LQ) foram de 7 a 62 pg mg-1 e 0,5 a 20 pg mg-1 para HS-SPME e HFLPME, respectivamente. O 9-THC apresentou valores de limites de quantificação para os dois métodos abaixo do valor de cut-off (LQ ≤ 100 pg mg-1). Finalmente, os métodos desenvolvidos e validados foram aplicados na determinação de CBD, 9- THC e CBN em amostras de cabelo de pacientes de centro de reabilitação de dependentes químicos. As concentrações dos canabinóides nas amostras variaram do limite de detecção a 18 pg mg-1 para CBD, do limite de detecção a 232 pg mg-1 para 9-THC e 9-300 pg mg-1 para CBN, demonstram a aplicabilidade do método em estudos de monitorização.

A lamotrigina (LTG) é um fármaco pertencente à classe das feniltriazinas utilizado no tratamento de crises epilépticas generalizadas e focais e no tratamento adjunto da epilepsia refratária. Devido à alta variabilidade interindividual, às interações medicamentosas e aos efeitos adversos apresentados durante a administração da LTG, a monitorização terapêutica nos pacientes que fazem uso deste fármaco é necessária para ajuste de dose individual e evitar os efeitos adversos. Assim, o objetivo deste trabalho foi a avaliação de duas técnicas de microextração: a microextração em fase líquida com fibras ocas (HF-LPME) e a microextração líquido-líquido dispersiva (DLLME) para análise da lamotrigina em amostras de plasma de pacientes epilépticos. Primeiramente foram definidas as condições eletroforéticas: foi utilizado um capilar de sílica fundida de 75 ?m de diâmetro interno e 50 cm de comprimento efetivo. O eletrólito de corrida (BGE) foi composto por ácido 2-morfolinoetanosulfônico (MES), na concentração de 130 mmol L-1 e pH 5,0. As análises foram realizadas à temperatura de 20°C e tensão de 15 kV. A amostra foi injetada hidrodinamicamente (0,5 psi por 10 s) e a detecção foi feita em 214 nm. Nestas condições a LTG e o padrão interno (PI), lidocaína, puderam ser analisados em menos de 7 minutos. A HF-LPME foi avaliada no modo de 3 fases, usando 500 ?L de plasma e 3,5 mL de solução fosfato de sódio 50 mmol L-1 pH 9,0 como fase doadora. O solvente utilizado para impregnar a fibra foi o 1-octanol. Como fase aceptora foram utilizados 60 ?L de solução de ácido clorídrico pH 4,0. Para avaliação da DLLME, foi necessária uma etapa de pré-tratamento da amostra (500 ?L de plasma) com 1 mL de acetonitrila. Após isto, 1,3 mL do sobrenadante foram adicionados a 4 mL de solução fosfato de sódio 50 mmol L-1 pH 9,0 e 120 ?L de clorofórmio (solvente extrator) foram injetados nesta amostra aquosa e 165 ?L de fase sedimentada foram recuperados. As características de desempenho analítico para ambos os métodos foram avaliadas, sendo obtida linearidade na faixa de concentração plasmática de 1-20 ?g/mL e limite inferior de quantificação (LIQ) de 1 ?g mL-1. Os ensaios de precisão e exatidão apresentaram valores de acordo com os guias oficiais. Além disso, os métodos foram seletivos, não apresentaram efeito residual e as amostras foram estáveis. Os valores de recuperação foram de 54,3 e 23% para HF-LPME e DLLME, respectivamente. Os métodos validados foram aplicados com sucesso em amostras de plasma de pacientes epilépticos em tratamento com a LTG. Além disso, as duas técnicas foram comparadas e a HF-LPME apresentou vantagens em relação à DLLME, mostrando ser uma técnica promissora para análise de matrizes complexas, com reduzido consumo de solvente orgânico e possibilidade de automação. / Lamotrigine (LTG) is an antiepileptic drug, which belongs to the class of phenyltriazine that can be used in the treatment of new-onset and refractory epilepsy. Due to its high interindividual variability, drug interactions and the adverse effects presented during the LTG administration, therapeutic drug monitoring is very important to dose adjustment and to avoid toxicity effects. Thus, the goal of this study was to develop and validate two microextraction techniques: the hollow fiber liquid-phase microextraction (HF-LPME) and the dispersive liquid-liquid microextraction (DLLME) to analyze LTG in plasma samples of epileptic patients. First of all, the eletroforetic conditions were optimized. A fused-silica uncoated capillary with 75 ?m internal diameter, and 50 cm effective length was used. The 2-(N-morpholino)ethanesulfonic acid (MES) 130 mmol L-1 pH 5.0 was chosen as background electrolyte (BGE). The temperature and the voltage were kept constant at 20°C and 15 kV respectively. For sample injection, hydrodynamic injection mode was used, with a pressure of 0.5 psi applied for 10 s. The wavelength was set at 214 nm. Under final conditions, LTG and the internal standard (IS) lidocaine were analyzed in less than 7 minutes. HF-LPME was evaluated in the three phase mode. The analyte was extracted from 4.0 mL of a basic donor phase (composed of 500 ?L of plasma and 3.5 mL of sodium phosphate solution 50 mmol L-1 pH 9.0) into an organic phase composed of 1-octanol immobilized in the pores of the hollow fiber, and further into an acidic acceptor phase (hydrochloric acid solution pH 4.0) placed in the lumen of the fiber. To evaluate DLLME, the plasma samples were pretreated to remove the proteins, and 500 ?L of plasma sample was mixed with 1 mL of acetonitrile. After that, 1,3 mL of the upper layer was added to 4 mL of sodium phosphate solution 50 mmol L-1 pH 9.0, and 120 ?L of chloroform (extracting solvent) was rapidly injected in the aqueous sample and 165 ?L of the sedimented phase was collected. Under the optimized conditions, both methods were linear over the plasmatic concentration range of 1.0-20.0 ?g mL-1 and the lower limit of quantification (LLOQ) was 1.0 ?g mL-1. Both methods showed good precision, accuracy, selectivity to LTG, with no carryover and the samples were stable under the studied conditions. The recovery were 54,3 and 23% to HF-LPME and DLLME respectively. The validated methods were successfully applied for the quantification of LTG in plasma samples of epileptic patients. The techniques were compared and HF-LPME was more advantageous for being more suitable to analysis of complex matrices using small amount of organic solvent, and also can be automated.

Syftet med examensarbetet har varit att hitta lämpliga textila material för en klimatsmart rullgardin med flera olika skikt skapad av företaget Climate Curtains, samt att ta fram en väl genomtänkt design som är anpassad för miljön den är tänkt att hänga i, nämligen skolor och kontor. Den klimatsmarta rullgardinen ska ha ett absorberande mattsvart material närmast glasfönstret för att fånga upp UV-strålning och därmed bli varmt. Värmen ska sedan föras in i rummet med hjälp av fläktar som sitter monterade inuti gardinstången. En solcellsfilm ska även fästas på skiktet närmast fönstret och har därför tagits med i beräkningarna, dock är solcellsfilmen fortfarande under utveckling. Tanken med solcellsfilmen är först och främst att den ska förse fläktarna med energi men även webbelysning eller laddning av mobil och dator vid överflöd av energi ska vara möjligt. Rullgardinen ska även ha ett vitt reflekterande material in mot rummet för att möjligheten att vända gardinen ska finnas. Under sommartid kan den vända gardinen istället reflektera bort UV-ljus. Mellan dessa två skikt ska ett antal mellanskikt hänga för att erhålla bättre isoleringsegenskaper samtidigt som buller och oljud minskas. Det har även varit relevant att undersöka om flamskyddsmedel bör användas eftersom att gardinen ska hänga i offentliga miljöer. Examensarbetet har bestått av litteraturstudier och praktiska experiment. Experimenten som utfördes var nöthärdighets-, flexibilitets-, reflektionstest samt säkerställning av färg. Materialen som har undersökts har alla varit gjorda av 100% polyester och två alternativa material valdes för vardera skikt. Polyester valdes till alla skikt dels för att det är billigt och dels för att polyester visade sig ha mycket goda egenskaper för de krav som ställdes. Ytterskiktet som är närmast glasfönstret samt innerskiktet in mot rummet valdes till vävar med olika bindningar. Till ytterskiktet jämfördes en tvåskaftsväv med en kypertväv där tvåskaftsväven uppvisade bäst resultat i alla testerna. Kypertväven färgade av sig och nöttes ner i nöthärdighetstestet vilket inte tvåskaftsväven gjorde. Flexibilitets- och reflektionstestet visade goda resultat för båda vävarna. I reflektionstestet pikade tvåskaftsvävens reflektionskurva en aning i det röda spektrat, vilket innebar att den hade en viss röd nyans i sig. Säkerställning av färg gick inte att utföra för de svarta vävarna då svart färg finns i oändligt många olika nyanser. Till det vita innerskiktet jämfördes en tvåskaftsväv med en satinväv. Båda vävarna hade relativt lika resultat i nöthärdighets- samt flexibilitetstestet men satinväven fick bättre resultat i reflektionstestet vilket var avgörande. Vid säkerställning av färg testades den vita färgen i ett ljusskåp i olika ljus för att kontrollera dess vithet. Det visade sig att båda vävarna innehöll optiskt vitmedel vilket även framkom i reflektionstestet då de reflekterade över 100 %. Till mellanskikten jämfördes två olika nonwovenmaterial som består av ihåliga polyesterfibrer. Ihåliga fibrer ha bra ljudabsorption vilket kan vara bra i miljöer såsom skolor och kontor där det kan vara mycket buller och höga ljudnivåer. Det ena materialet vägde 100g/m2 och det andra 250g/m2. Ett nöthärdighets- och flexibilitetstest utfördes på dessa nonwovenmaterial. De båda fick godkänt resultat i flexibilitetstestet men nonwoven 100 höll inte måttet i nöthärdighetstestet varav nonwoven 250 är mest lämpat för rullgardinen. Litteraturstudiens resultat tyder på att det inte finns några krav på flamskyddsmedel i gardiner i offentlig miljö utan endast rekommendationer. Det är alltså upp till företag att bestämma om de vill flamskydda gardinerna. De finns en mängd olika flamskyddsmedelsvarianter men de har alla en sak gemensamt och det är att de är fettlösliga och långlivade, vilket gör att de är svåra att bryta ned. Gardinen designades i en stilren och klassisk design. En kornisch utformades dels för att dölja gardinstången och dels för att erhålla ett snyggare helhetsintryck. Gardinen kommer att ha en fåll längst ned på det yttre och det inre skiktet. Inuti fållen kommer en plastskena läggas för att få tyngd i materialet och därmed ett bättre fall. Fållen ger även gardinen en lyxigare känsla. Resterande kanter på alla materialen för alla skikt valdes att lasras. Med laserskärning erhålls fina kanter som inte fransar sig alls och laserskärning garanterar även att det inte blir någon nötning på produkten under skärningen vilket är fördelaktigt på en rullgardin då den rullas upp och ner mycket. Skisser ritades upp i Kaledo Style för att få en tydligare bild av hur rullgardinen kan komma att se ut. Eventuella tillval, mönster på det vita skiktet samt solceller i olika storlekar, kan även göras på gardinen beroende på kundens önskemål. För att kunna applicera mönstret på det textila materialet undersöktes tre alternativa tryckmönstermetoder; rollerprinting, roterande screentryck samt digital inktryck. De två sistnämnda lämpar sig bäst för ändamålet. / The aim of the thesis was to find the optimal textile materials for a climate-smart blind with multiple layers created by the company Climate Curtains. The aim was also to develop a well thought out design that is adapted to the environments it is supposed to hang in, which are schools and offices. The climate-smart blind should have an absorbing black matte material closest to the glass window to capture UV radiation and thereby become warm. The heat will then be brought into the room with the help of fans that are mounted inside the curtain rod. A solar cell film should also be attached to the layer closest to the window and have therefore been included in the calculations, however, the solar film is still under development. The idea of a solar cell film is first and foremost that it will provide fans with energy but also charging of mobile and computer at the abundance of energy. The blind must also have a white reflective material into the room for the possibility of turning the curtain in the summer. This leads to a reflection of the UV light instead of absorption. Between these two layers, a number of intermediate layers will hang to provide isolation of air and noise reduction. The amount of flame retardants have also been relevant to examine because the curtain will hang in public places. There are no requirements in public places when it comes to flame retardants, but there are recommendations published. A solar cell film should also be attached to the layer closest to the window and have therefore been included in the calculations. However, the solar film is still under development. The work has consisted of literature studies, laboratory work and compilation of discussion and results. The laboratory work included abrasion resistance-, flexibility-, reflection test and a test to secure the colors. The materials studied have all been made of 100% polyester and two alternative materials were chosen for each layer. Polyester was chosen to all layers partly because it is cheap and secondly because polyester was found to have very good qualities for the demands made. The outer layer closest to the window and the inner layer into the room consists of fabrics made of weaves with different constructions. For the outer layer a plain weave and a twill weave were chosen to be compared against each other. The plain weave got the best results in all of the tests. For the inner layer a satin weave and a plain weave were compared, and the satin weave got the best results in all the tests. Furthermore, the layers in between the weave textiles are made of hollow polyester fibers as a nonwoven material. Hollow fibers have good sound absorption, which can be useful in environments such as schools and offices where there may be much noise and high sound levels. One material weighing 100 g/m2 and the other 250 g/m2. An abrasion resistance- and flexibility test was conducted on these nonwoven materials. They both got approved results in the flexibility test. However, nonwoven 100 was not good enough in the abrasion resistance test and therefor nonwoven 250 is the most suitable middle layer for the blind. The curtain was designed in a stylish and classic design. A cornice designed partly to hide the curtain rod and partly to obtain a more attractive overall impression. The blind will have a hem at the bottom of the outer and the inner layer. Inside the hem a plastic splint is added to give better stability. The hem also gives the curtain a luxurious feel. The remaining edges on all materials for all layers were chosen to be lasered. With laser cutting fine edges are obtained.4Sketches were drawn up in Kaledo Style to get a clearer picture of how the blind could look like. Any optional patterns on the white layer and the solar cells of different sizes, can also be made on the curtain, depending on customer requirements. In order to apply the pattern to the textile material three alternative methods was studied; roller printing, rotary screen printing and digital ink print. Screenprinting and digital printing was best suited for the purpose.

In this thesis, several types of scaffolds composed of different materials and designed structures and functions were fabricated by 3D plotting under mild conditions (room temperature and without using any organic solvent). Broad biomaterials including inorganic (such as calcium phosphate cement and mesoporous bioglass), organic (such as alginate and gelatin) and composite materials were prepared into printable pastes to plot as 3D scaffolds for bone tissue engineering. Organic/inorganic biphasic and bipartite structure, core/shell alginate/nano-hydroxyapatite and hollow fiber structure were designed and realized. Scaffolds with multi functions including suitable mechanical properties, sustained drug/protein delivery and in vitro vascularization were achievable. 3D plotting provided great achievements in the field of tissue engineering by preparing advanced scaffolds, as well as by plotting cell/matrix constructs, and even complex tissues and organs.