Ionic liquids for application in separation processes: chromatographic and calorimetric studies

Mestrado de dupla diplomação com a UTFPR - Universidade Tecnológica Federal do ParanáThe family of ionic liquids can provide safer, efficient and more sustainable alternative solvents than those commonly used. In this work, 1-butyl-3-methylimidazolium acetate (BmimAc) was the selected ionic liquid to be studied as a separation agent in different liquid-liquid extraction problems with terpenes and terpenoids. After separation, it is important to devise a strategy to recover the IL and minimize costs. To do so, infinite dilution activity coefficients of water and 44 solutes belonging to different families of organic compounds, were measured in the ionic liquid by gas chromatography. This ionic liquid showed strong interaction with polar solutes like alcohols and linalool, for which low values of activity coefficients at infinite dilution were obtained. Concerning the system limonene/linalool (compounds used in biodegradable solvents and perfumery industries), this IL showed the best values of capacity and selectivity, calculated through activity coefficients. However, it was not a good separation agent of the mixture α–pinene/β–pinene (used in used in medications with antifungal action). Besides that, the solid-liquid equilibria phase diagram was studied by differential scanning calorimetry (DSC), by measuring the freezing point depression of water caused by the addition of 1-butyl-3-methylimidazolium acetate. The methodology was tested first by measuring the freezing point of aqueous solutions of NaCl, CaCl2, 2-propanediol and 1-ethyl-3-methylimidazolium acetate (EmimAc). The values obtained in this work agreed with literature, except for the 1-ethyl-3-methylimidazolium acetate. So, further tests need to be carried out using other methodologies. Through the measurement of freezing point curves, important data were obtained concerning the 1-butyl-3-methylimidazolium acetate (BmimAc)+ water interactions. Thus, crystallization is a possible process for separating ILs from water. This work offers a solution to separate the system limonene/linalool and then recovery the IL through freezing point depression of water/BmimAc once that was possible freeze the water.A família de líquidos iônicos pode fornecer solventes alternativos mais seguros, eficientes e mais sustentáveis do que os comumente usados. Neste trabalho, acetato de 1-butil-3-metilimidazólio (BmimAc) foi o líquido iônico selecionado para ser estudado como um agente de separação em diferentes problemas de extração líquido-líquido com terpenos e terpenóides. Após a separação, é importante conceber uma estratégia para recuperar o LI e minimizar os custos. Para isso, foram medidos coeficientes de atividade a diluição infinita de água e 44 solutos pertencentes a diferentes famílias de compostos orgânicos, no líquido iônico, por cromatografia gasosa. Este líquido iônico mostrou forte interação com solutos polares como álcoois e linalol, para os quais foram obtidos baixos valores de coeficientes de atividade em diluição infinita. No que diz respeito ao sistema limoneno / linalol (compostos utilizados como solventes biodegradáveis e na indústria de perfumaria), este IL mostrou os melhores valores de capacidade e seletividade. No entanto, não foi um bom agente de separação da mistura α-pineno / β-pineno (usados em medicamentos com ação anti-fungica). Além disso, o diagrama de fases de equilíbrio sólido-líquido foi estudado por calorimetria diferencial de varredura (DSC), medindo a depressão do ponto de congelamento da água causada pela adição de acetato de 1-butil-3-metilimidazólio. A metodologia foi testada primeiro medindo o ponto de congelamento de soluções aquosas de NaCl, CaCl2, 2-propanodiol e acetato de 1-etil-3-metilimidazólio (EmimAc). Os valores obtidos neste trabalho concordam com a literatura, exceto o acetato de 1-etil-3-metilimidazólio. Portanto, testes adicionais precisam ser realizados usando outras metodologias. Através da medição das curvas do ponto de congelamento, foram obtidos dados importantes sobre as interações 1-butil-3-metilimidazólio + água. Assim, a cristalização é um processo possível para separar ILs da água. Este trabalho oferece uma solução para a separação do sistema limoneno/linalol e a recuperação do LI usado no sistema por meio do abaixamento do ponto de congelamento da água em contato com o BmimAc, uma vez que foi possível cristalizar a água da mistura

Despesa com pessoal após a lei de responsabilidade fiscal: sua observância aos limites do município de Governador Celso Ramos no período de 2015 a 2017.

TCC (Graduação) - Universidade Federal de Santa Catarina. Centro Socioeconômico. Ciências Contábeis.As despesas com pessoal são as que mais aguçam a atenção dos cidadãos e dos entes públicos. Uma de suas condições mais questionadas tem sido a limitação para despesas com pessoal. Dessa forma, torna-se relevante conhecer o comportamento de tais despesas e a observância aos limites da Lei de Responsabilidade Fiscal (LRF), nos entes públicos, em particular no município de Governador Celso Ramos (GCR) do estado de Santa Catarina (SC). Nesse sentido, este trabalho tem como objetivo evidenciar o desempenho do Município, nos Poderes Executivo e Legislativo, em relação ao cumprimento dos limites específicos de despesa com pessoal em face da LRF, por meio da análise dos dados disponibilizados no portal de transparência pelo Tribunal de Contas do Estado de Santa Catarina (TCE/SC) e pelo ente, nos anos 2017, 2018 e 2019. Adicionalmente, procedeu-se a ajustes monetários dos valores, conforme o Índice Nacional de Preços ao Consumidor Amplo (IPCA), com vistas a uma melhor evidenciação do objeto desta pesquisa. Além do limite máximo, foram analisados os limites prudencial e de alerta. Na separação dos Poderes, constatou-se que o Poder Executivo é o maior responsável pelos gastos de despesa com pessoal, tanto em valores absolutos quanto em proporção ao limite da LRF. Em relação aos resultados da pesquisa, verificou-se que GCR cumpriu os limites máximo e prudencial, ficando somente o limite de alerta ultrapassado em um dos Poderes, o Executivo; porém, nenhum limite foi excedido pelo Poder Legislativo. Ademais, as limitações impostas pela LRF tornaram o controle das despesas com pessoal mais eficiente e têm contribuído para uma gestão responsável e transparente

Ionic liquids as entrainers for terpenes fractionation and other relevant separation problems

This work discusses the potential of two phosphonium-based ionic liquids (ILs), [P6,6,6,14]Cl and [P6,6,6,14][(C8H17)2PO2], and one methylimidazolium-based IL, [C4mim][OAc], as entrainers in the fractionation of terpene mixtures, in the desulfurization and denitrification of fuel oils, and in the separation of aromatics from aliphatic hydrocarbons. To this aim, the activity coefficients at infinite dilution of 45 solutes were obtained by gas-chromatography in the temperature range (333.15–458.15) K. Selectivities and capacities were calculated showing that [P6,6,6,14]Cl is adequate for the fractionation of (−)-menthone/L-(−)-menthol mixture, being also a suitable option for the deterpenation of citrus essential oil, and the removal of thiophene and pyridine from aliphatic hydrocarbons. To complement the experimental measurements COSMO-RS model was tested, demonstrating good potential to screen separation agents and give insights for several important separation problems, including the removal of contaminants from fuels and the isolation, fractionation and purification of terpenes mixtures.This work was developed within the scope of the project CICECOAveiro Institute of Materials, UIDB/50011/2020 & UIDP/50011/2020, and CIMO-Mountain Research Center, UIDB/00690/2020, both financed by national funds through the Portuguese Foundation for Science and Technology/MCTES. Sérgio M. Vilas-Boas also thanks FCT for the Ph.D. grant (SFRH/BD/138149/2018).info:eu-repo/semantics/publishedVersio

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Representation of capacity drop at a road merge via point constraints in a first order traffic model

We reproduce the capacity drop phenomenon at a road merge by implementing a non-local point constraint at the junction in a first order traffic model. We call capacity drop the situation in which the outflow through the junction is lower than the receiving capacity of the outgoing road, as too many vehicles trying to access the junction from the incoming roads hinder each other. In this paper, we first construct an enhanced version of the locally constrained model introduced by Haut et al. (Proceedings 16th IFAC World Congress. Prague, Czech Republic 229 (2005) TuM01TP/3), then we propose its counterpart featuring a non-local constraint and finally we compare numerically the two models by constructing an adapted finite volumes scheme

Relevance of <i>ARID1A</i> Mutations in Endometrial Carcinomas

Since the Cancer Genome Atlas (TCGA) project identified four distinct groups based on molecular alterations, mutation analyses have been integrated into the characterization of endometrial carcinomas (ECs). ARID1A seems to be the subunit more involved in the loss of function of the SWI/SNF complex in ECs. The aim of this study is to define the relevance of ARID1A alterations in a cohort of EC, studying the possible associations between DNA mutation (genomic level), RNA expression (transcriptomic level), and protein expression (proteomic level). A total of 50 endometrial carcinomas were characterized for ARID1A mutations (using targeted DNA next-generation sequencing—NGS), ARID1A gene expression (using RNAseq and qRT-PCR), and ARID1A protein expression (using immunohistochemistry—IHC). Moreover, we have investigated if ARID1A mutations may alter the protein structure, using the Protein Data Bank sequence. We found a good correlation between ARID1A mutations and protein immunostaining, even if we did not find statistically significant differences in the ARID1A expression levels. In conclusion, our data demonstrated that the molecular characterization of ARID1A should be associated with IHC analysis, mainly in those cases harboring “novel” ARID1A mutations or in those alterations with “uncertain” pathogenic significance

"Delirium Day": A nationwide point prevalence study of delirium in older hospitalized patients using an easy standardized diagnostic tool

Background: To date, delirium prevalence in adult acute hospital populations has been estimated generally from pooled findings of single-center studies and/or among specific patient populations. Furthermore, the number of participants in these studies has not exceeded a few hundred. To overcome these limitations, we have determined, in a multicenter study, the prevalence of delirium over a single day among a large population of patients admitted to acute and rehabilitation hospital wards in Italy. Methods: This is a point prevalence study (called "Delirium Day") including 1867 older patients (aged 65 years or more) across 108 acute and 12 rehabilitation wards in Italian hospitals. Delirium was assessed on the same day in all patients using the 4AT, a validated and briefly administered tool which does not require training. We also collected data regarding motoric subtypes of delirium, functional and nutritional status, dementia, comorbidity, medications, feeding tubes, peripheral venous and urinary catheters, and physical restraints. Results: The mean sample age was 82.0 ± 7.5 years (58 % female). Overall, 429 patients (22.9 %) had delirium. Hypoactive was the commonest subtype (132/344 patients, 38.5 %), followed by mixed, hyperactive, and nonmotoric delirium. The prevalence was highest in Neurology (28.5 %) and Geriatrics (24.7 %), lowest in Rehabilitation (14.0 %), and intermediate in Orthopedic (20.6 %) and Internal Medicine wards (21.4 %). In a multivariable logistic regression, age (odds ratio [OR] 1.03, 95 % confidence interval [CI] 1.01-1.05), Activities of Daily Living dependence (OR 1.19, 95 % CI 1.12-1.27), dementia (OR 3.25, 95 % CI 2.41-4.38), malnutrition (OR 2.01, 95 % CI 1.29-3.14), and use of antipsychotics (OR 2.03, 95 % CI 1.45-2.82), feeding tubes (OR 2.51, 95 % CI 1.11-5.66), peripheral venous catheters (OR 1.41, 95 % CI 1.06-1.87), urinary catheters (OR 1.73, 95 % CI 1.30-2.29), and physical restraints (OR 1.84, 95 % CI 1.40-2.40) were associated with delirium. Admission to Neurology wards was also associated with delirium (OR 2.00, 95 % CI 1.29-3.14), while admission to other settings was not. Conclusions: Delirium occurred in more than one out of five patients in acute and rehabilitation hospital wards. Prevalence was highest in Neurology and lowest in Rehabilitation divisions. The "Delirium Day" project might become a useful method to assess delirium across hospital settings and a benchmarking platform for future surveys

Understanding Factors Associated With Psychomotor Subtypes of Delirium in Older Inpatients With Dementia

Objectives: Few studies have analyzed factors associated with delirium subtypes. In this study, we investigate factors associated with subtypes of delirium only in patients with dementia to provide insights on the possible prevention and treatments. Design: This is a cross-sectional study nested in the \u201cDelirium Day\u201d study, a nationwide Italian point-prevalence study. Setting and Participants: Older patients admitted to 205 acute and 92 rehabilitation hospital wards. Measures: Delirium was evaluated with the 4-AT and the motor subtypes with the Delirium Motor Subtype Scale. Dementia was defined by the presence of a documented diagnosis in the medical records and/or prescription of acetylcholinesterase inhibitors or memantine prior to admission. Results: Of the 1057 patients with dementia, 35% had delirium, with 25.6% hyperactive, 33.1% hypoactive, 34.5% mixed, and 6.7% nonmotor subtype. There were higher odds of having venous catheters in the hypoactive (OR 1.82, 95% CI 1.18-2.81) and mixed type of delirium (OR 2.23, CI 1.43-3.46), whereas higher odds of urinary catheters in the hypoactive (OR 2.91, CI 1.92-4.39), hyperactive (OR 1.99, CI 1.23-3.21), and mixed types of delirium (OR 2.05, CI 1.36-3.07). We found higher odds of antipsychotics both in the hyperactive (OR 2.87, CI 1.81-4.54) and mixed subtype (OR 1.84, CI 1.24-2.75), whereas higher odds of antibiotics was present only in the mixed subtype (OR 1.91, CI 1.26-2.87). Conclusions and Implications: In patients with dementia, the mixed delirium subtype is the most prevalent followed by the hypoactive, hyperactive, and nonmotor subtype. Motor subtypes of delirium may be triggered by clinical factors, including the use of venous and urinary catheters, and the use of antipsychotics. Future studies are necessary to provide further insights on the possible pathophysiology of delirium in patients with dementia and to address the optimization of the management of potential risk factors