Overcoming performance and convergence issues of discrete transform based modeling of crosslinking classical and reversible deactivated radical polymerizations

Population balances of polymer species in terms 'of discrete transforms with respect to counts of groups lead to tractable first order partial differential equations when ali rate constants are independent of chain length and loop formation is negligible [l]. Average molecular weights in the absence ofgelation are long known to be readily found through integration of an initial value problem. The extension to size distribution prediction is also feasible, but its performance is often lower to the one provided by methods based upon real chain length domain [2]. Moreover, the absence ofagood starting procedure and a higher numerical sensitivity hás decisively impaired its application to non-linear reversibly deactivated polymerizations, namely NMRP [3].

Grafting of functional brushes on the surface of 5-Fluorouracil molecularly imprinted polymer particles through RAFT polymerization

The grafting of functional brushes on the surface of molecularly imprinted polymer (MIP). particles hás been explored in the last few years to synthesize materiais combining high molecular recognition capabilities and stimulation triggered by changes in the surrounding environment [1, 2]. In the present work, MIP particles for 5-fluorouracil (a drug used in câncer treatment) were produced by precipitation polymerization in acetonitrile, using either MAA or HEMA as imprinting fünctional monomers, and m the presence of different kinds of RAFT agents. In a second step, taking advantage of the RAFT groups present in the surface of the particles, different kinds of fiinctional polymer brushes were grafted on the MIPs considering a "grafting from" process in the presence of a RAFT agent.

Growth, viral production and metabolism of a Helicoverpa zea cell line in serum-free culture

Insect cell cultures have been extensively utilised for means of production for heterologous proteins and biopesticides. Spodoptera frugiperda (Sf9) and Trichoplusia ni (High Five(TM)) cell lines have been widely used for the production of recombinant proteins, thus metabolism of these cell lines have been investigated thoroughly over recent years. The Helicoverpa zea cell line has potential use for the production of a biopesticide, specifically the Helicoverpa armigera single-nucleocapsid nucleopolyhedrovirus (HaSNPV). The growth, virus production, nutrient consumption and waste production of this cell line was investigated under serum-free culture conditions, using SF900II and a low cost medium prototype (LCM). The cell growth ( growth rates and population doubling time) was comparable in SF900II and LCM, however, lower biomass and cell specific virus yields were obtained in LCM. H. zea cells showed a preference for asparagine over glutamine, similar to the High Five(TM) cells. Ammonia was accumulated to significantly high levels (16 mM) in SF900II, which is an asparagine and glutamine rich medium. However, given the absence of asparagine and glutamine in the medium ( LCM), H. zea cells adapted and grew well in the absence of these substrates and no accumulation of ammonia was observed. The adverse effect of ammonia on H. zea cells is unknown since good production of biologically active HaSNPV was achieved in the presence of high ammonia levels. H. zea cells showed a preference for maltose even given an abundance supply of free glucose. Accumulation of lactate was observed in H. zea cell cultures.

Measurement of implicit leadership theories and their effect on leadership processes and outcomes

The leadership categorisation theory suggests that followers rely on a hierarchical cognitive structure in perceiving leaders and the leadership process, which consists of three levels; superordinate, basic and subordinate. The predominant view is that followers rely on Implicit Leadership Theories (ILTs) at the basic level in making judgments about managers. The thesis examines whether this presumption is true by proposing and testing two competing conceptualisations; namely the congruence between the basic level ILTs (general leader) and actual manager perceptions, and subordinate level ILTs (job-specific leader) and actual manager. The conceptualisation at the job-specific level builds on context-related assertions of the ILT explanatory models: leadership categorisation, information processing and connectionist network theories. Further, the thesis addresses the effects of ILT congruence at the group level. The hypothesised model suggests that Leader-Member Exchange (LMX) will act as a mediator between ILT congruence and outcomes. Three studies examined the proposed model. The first was cross-sectional with 175 students reporting on work experience during a 1-year industrial placement. The second was longitudinal and had a sample of 343 students engaging in a business simulation in groups with formal leadership. The final study was a cross-sectional survey in several organisations with a sample of 178. A novel approach was taken to congruence analysis; the hypothesised models were tested using Latent Congruence Modelling (LCM), which accounts for measurement error and overcomes the majority of limitations of traditional approaches. The first two studies confirm the traditional theorised view that employees rely on basic-level ILTs in making judgments about their managers with important implications, and show that LMX mediates the relationship between ILT congruence and work-related outcomes (performance, job satisfaction, well-being, task satisfaction, intragroup conflict, group satisfaction, team realness, team-member exchange, group performance). The third study confirms this with conflict, well-being, self-rated performance and commitment as outcomes.

Heterogenitás és technikai hatékonyság - a magyar specializált szántóföldi növénytermesztő üzemek esete = Heterogeneity and technical efficiency - the case of Hungary's specialized arable crop production units

A cikkben paneladatok segítségével a magyar gabonatermesztő üzemek 2001 és 2009 közötti technikai hatékonyságát vizsgáljuk. A technikai hatékonyság szintjének becslésére egy hagyományos sztochasztikus határok modell (SFA) mellett a látens csoportok modelljét (LCM) használjuk, amely figyelembe veszi a technológiai különbségeket is. Eredményeink arra utalnak, hogy a technológiai heterogenitás fontos lehet egy olyan ágazatban is, mint a szántóföldi növénytermesztés, ahol viszonylag homogén technológiát alkalmaznak. A hagyományos, azonos technológiát feltételező és a látens osztályok modelljeinek összehasonlítása azt mutatja, hogy a gabonatermesztő üzemek technikai hatékonyságát a hagyományos modellek alábecsülhetik. _____ The article sets out to analyse the technical efficiency of Hungarian crop farms between 2001 and 2009, using panel data and employing both standard stochastic frontier analysis and the latent class model (LCM) to estimate technical efficiency. The findings suggest that technological heterogeneity plays an important role in the crop sector, though it is traditionally assumed to employ homogenous technology. A comparison of standard SFA models that assumes the technology is common to all farms and LCM estimates highlights the way the efficiency of crop farms can be underestimated using traditional SFA models.

Design, modelling, simulation and integration of cyber physical systems: methods and applications

The main drivers for the development and evolution of Cyber Physical Systems (CPS) are the reduction of development costs and time along with the enhancement of the designed products. The aim of this survey paper is to provide an overview of different types of system and the associated transition process from mechatronics to CPS and cloud-based (IoT) systems. It will further consider the requirement that methodologies for CPS-design should be part of a multi-disciplinary development process within which designers should focus not only on the separate physical and computational components, but also on their integration and interaction. Challenges related to CPS-design are therefore considered in the paper from the perspectives of the physical processes, computation and integration respectively. Illustrative case studies are selected from different system levels starting with the description of the overlaying concept of Cyber Physical Production Systems (CPPSs). The analysis and evaluation of the specific properties of a sub-system using a condition monitoring system, important for the maintenance purposes, is then given for a wind turbine.

Língua eletrónica: uma ferramenta prática na análise sensorial de azeitonas de mesa

As azeitonas de mesa são consumidas e apreciadas em todo o mundo e, embora a sua classificação comercial não seja legalmente exigida, o Conselho Oleícola Internacional sugere que seja regulamentada com base na avaliação sensorial por um painel de provadores. A implementação de tal requer o cumprimento de diretrizes estabelecidas pelo Conselho Oleícola Internacional, resultando numa tarefa complexa, demorada e cujas avaliações não estão isentas de subjetividade. Neste trabalho, pela primeira vez, uma língua eletrónica foi utilizada com o intuito de classificar azeitonas de mesa em categorias comerciais, estipuladas com base na presença e na mediana das intensidades do defeito organolético predominante percebido pelo painel de provadores. Modelos de discriminação lineares foram estabelecidos com base em subconjuntos de sinais potenciométricos de sensores da língua eletrónica, selecionados recorrendo ao algoritmo de arrefecimento simulado. Os desempenhos qualitativo de previsão dos modelos de classificação estabelecidos foram avaliados recorrendo à técnica de validação cruzada leave-one-out e à técnica de validação cruzada K-folds com repetição, que permite minimizar o risco de sobreajustamento, permitindo obter resultados mais realistas. O potencial desta abordagem qualitativa, baseada nos perfis eletroquímicos gerados pela língua eletrónica, foi satisfatoriamente demonstrado: (i) na classificação correta (sensibilidades ≥ 93%) de soluções padrão (ácido n-butírico, 2-mercaptoetanol e ácido ciclohexanocarboxílico) de acordo com o defeito sensorial que mimetizam (butírico, pútrido ou sapateira); (ii) na classificação correta (sensibilidades ≥ 93%) de amostras de referência de azeitonas e salmouras (presença de um defeito único intenso) de acordo com o tipo de defeito percebido (avinhado-avinagrado, butírico, mofo, pútrido ou sapateira), e selecionadas pelo painel de provadores; e, (iii) na classificação correta (sensibilidade ≥ 86%) de amostras de azeitonas de mesa com grande heterogeneidade, contendo um ou mais defeitos organoléticos percebidos pelo painel de provadores nas azeitona e/ou salmouras, de acordo com a sua categoria comercial (azeitona extra sem defeito, extra, 1ª escolha, 2ª escolha e azeitonas que não podem ser comercializadas como azeitonas de mesa). Por fim, a capacidade língua eletrónica em quantificar as medianas das intensidades dos atributos negativos detetados pelo painel nas azeitonas de mesa foi demonstrada recorrendo a modelos de regressão linear múltipla-algoritmo de arrefecimento simulado, com base em subconjuntos selecionados de sinais gerados pela língua eletrónica durante a análise potenciométrica das azeitonas e salmouras. O xii desempenho de previsão dos modelos quantitativos foi validado recorrendo às mesmas duas técnicas de validação cruzada. Os modelos estabelcidos para cada um dos 5 defeitos sensoriais presentes nas amostras de azeitona de mesa, permitiram quantificar satisfatoriamente as medianas das intensidades dos defeitos (R² ≥ 0,97). Assim, a qualidade satisfatória dos resultados qualitativos e quantitativos alcançados permite antever, pela primeira vez, uma possível aplicação prática das línguas eletrónicas como uma ferramenta de análise sensorial de defeitos em azeitonas de mesa, podendo ser usada como uma técnica rápida, económica e útil na avaliação organolética de atributos negativos, complementar à tradicional análise sensorial por um painel de provadores.

Eliminação/valorização de resíduos de frutas (kiwi) por digestão anaeróbia

Este estudo tem como objetivo a valorização económica de resíduos agroindustriais, nomeadamente resíduos de kiwi, por digestão anaeróbia de forma a otimizar a produção de biogás e a sua qualidade (% CH4). Trata-se de uma pesquisa experimental que consistiu na avaliação da produção de biogás usando diferentes proporções de substrato e inóculo, quatro valores distintos para a razão C:N, inóculo de diferentes digestores e colheita do inóculo em épocas distintas do ano. Os ensaios foram desenvolvidos num reator batch em condições mesofílicas, sendo o processo acompanhado por monitorização dos parâmetros: pH, Alcalinidade, Ácidos Gordos Voláteis (AGV), Sólidos Totais (ST), Sólidos Voláteis (SV), Carência Química de Oxigénio (CQO) e Carbono. Para a totalidade dos ensaios, o valor de pH no reator praticamente não apresentou variação, mantendo-se em torno de 7,0; a alcalinidade do meio, 1500 mg CaCO3/L, revelou-se adequada uma vez que no final do processo de DA a concentração de AGV (400-600 mg/L), nunca excede os valores considerados críticos. Os resultados obtidos apresentam valores interessantes para um número considerável de ensaios. Das 10 experiências realizadas, em duas foram obtidos resultados muito significativos em relação à literatura; o ensaio com 1% de substrato (experiência 2) registou uma produção de biogás de 1628 L/kg SV com uma %CH4 de 57% e o biogás de maior qualidade, 85% de metano, foi obtido no ensaio com 5% de resíduo de kiwi (experiência 10). As experiências em que se avaliou o efeito da razão C:N foram as menos produtivas, possivelmente devido à inibição da atividade da população microbiana pelo KNO3. A qualidade do inóculo revelou-se determinante num conjunto de ensaios, nomeadamente quando a sua colheita foi realizada no inverno, com o digestor a apresentar temperaturas bastante baixas. De acordo com os valores mais favoráveis para a produção de biogás, por tonelada de resíduo de kiwi poderá ser obtido um valor monetário bruto de 102 €, resolvendo-se um problema de eliminação deste resíduo, com valorização energética simultaneamente.

Signs and Symptoms of Dry Eye in Keratoconus Patients: A Pilot Study

Purpose: To compare signs and symptoms of dry eye in keratoconus (KC) patients versus healthy subjects. Methods: A total of 15 KC patients (KC group, n = 15 eyes) and 16 healthy subjects (control group, 16 eyes) were enrolled in this study. The Schirmer I test with no anesthetic, tear break-up time (TBUT), corneal staining characteristics, and ocular surface disease index (OSDI) scores were evaluated for both groups. Impression cytology, combined with/scanning laser confocal microscopy (LCM), was performed to evaluate goblet cell density, mucin cloud height (MCH), and goblet cell layer thickness (CLT). Finally, tear concentrations of di-adenosine tetraphosphate (Ap4A) were assessed. Results were statistically analyzed using Shapiro–Wilk and non-parametric Wilcoxon rank sum tests. Statistical significance was set at p < 0.05. Results: KC patients had lower tear volumes and greater corneal staining than did healthy subjects (p < 0.05). OSDI scores were 44.96 ± 8.65 and 17.78 ± 6.50 for the KC and control groups, respectively (p < 0.05). We found no statistically significant differences in TBUT between groups. Impression cytology revealed lower goblet cell densities in KC group patients versus control group subjects (84.88 ± 32.98 and 128.88 ± 50.60 cells/mm,2 respectively, p < 0.05). There was a statistically significant reduction in MCH and CLT in KC group patients compared with control group subjects. Ap4A tear concentrations were higher in KC group patients than in control group subjects (2.56 ± 1.10 and 0.15 ± 0.12 µM, respectively, p < 0.05). Conclusions: The parameters evaluated in this study indicate that KC patients suffer greater symptoms of dry eye and greater tear instability, primarily due to the decreased mucin production in their tears, than do healthy patients with no KC.

Amphiphilic catalysts for the treatment of oily wastewaters

The main objective of this study was to obtain an effective catalyst for removal of diazo dye - Sudan IV by Catalytic Wet Peroxide Oxidation (CWPO). For this purpose liquid phase treatment was used to increase the basicity of activated carbon surface favoring the adsorption of organic pollutants. Modified activated carbon catalysts were used in different types of experiments: 1) decomposition of H2O2 in aquatic media, 2) decomposition of H2O2 in organic media, 3) adsorption of Sudan IV, 4) Sudan IV removal by CWPO. As the result of all of these experiments the most effective catalyst was obtained and discussed. It was not observed removal of Sudan IV from biphasic system by CWPO. The obtained results in some cases show a slight increase in concentration of Sudan IV, which may be ascribed to experimental errors. Different factors could be the reason of those errors. For example, the high volatility properties of organic media used in experiments should be taken into account during experiments. Under settled reaction temperature the decrease of cyclohexane volume during experiment could give rise in Sudan IV concentration. The initial concentration of model diazo dye also should be reviewed more detailed for CWPO experiments. Despite of these experimental errors the behavior of our catalysts in different media was observed.

Studies on terpenes solubility in water and deep eutectic solvents diagrams for biomedical applications

The main objectives of this work are the measurement of terpenes solubility in water at different temperatures, and the formulation of Deep Eutectic Solvents based on choline chloride and polycarboxylic acids, that can be used as hydrotropes of aqueous solutions in terpenes, replacing conventional organic solvents. In this work a new experimental methodology was implemented, using dialysis membranes, for the measurement of terpenes solubility in water. Concerning the deep eutectic diagrams formulation, the determination of the melting points of the eutectic mixtures was performed using a visual method. The method used for determining solubilities was previously validated using a well-studied model compound, toluene. The experimental results of terpenes solubilities in water resulted in a very satisfactory coefficients of variation, always below 6%. The experimental solubility data were analysed and the temperature dependence is also studied in a thermodynamic perspective. The compound with the largest solubility dependence with the temperature is geraniol, while thymol presents the smallest. The phase diagrams of DES formulated were quite satisfactory, presenting always eutectic points below to 373.15 K. For some compositions, the systems composed by choline chloride and lactic, or malonic, or myristic acid were liquid at room temperature. In the case of monocarboxylic acids, eutectic is formed at 60% mol of the acid, to dicarboxylic acid is formed at 50% mol of the acid and for tricarboxylic acid these point is formed at 30% mol of the acid. In the future, it will be important to study the effect of DES as hydrotropes in aqueous solutions of terpenes. Furthermore, it would be interesting to study more terpenes in order to assess the effect of the size of the alkyl chain and the structures of the compounds.

Probing the interactions between ionic liquids and water: experimental and quantum chemical approach

For an adequate choice or design of ionic liquids, the knowledge of their interaction with other solutes and solvents is an essential feature for predicting the reactivity and selectivity of systems involving these compounds. In this work, the activity coefficient of water in several imidazolium-based ionic liquids with the common cation 1-butyl-3-methylimidazolium was measured at 298.2 K. To contribute to a deeper insight into the interaction between ionic liquids and water, COSMO-RS was used to predict the activity coefficient of water in the studied ionic liquids along with the excess enthalpies. The results showed good agreement between experimental and predicted activity coefficient of water in ionic liquids and that the interaction of water and ionic liquids was strongly influenced by the hydrogen bonding of the anion with water. Accordingly, the intensity of interaction of the anions with water can be ranked as the following: [CF3SO3](-) < [SCN](-) < [TFA](-) < Br(-) < [TOS](-) < Cl(-) < [CH3SO3](-) [DMP](-) < [Ac](-). In addition, fluorination and aromatization of anions are shown to reduce their interaction with water. The effect of temperature on the activity coefficient of water at infinite dilution was measured by inverse gas chromatography and predicted by COSMO-RS. Further analysis based on COSMO-RS provided information on the nature of hydrogen bonding between water and anion as well as the possibility of anion-water complex formation.

Evaluation of the conductor-like screening model for real solvents for the prediction of the water activity coefficient at infinite dilution in ionic liquids

Ionic liquids (ILs) have attracted great attention, from both industry and academia, as alternative fluids for very different types of applications. The large number of cations and anions allow a wide range of physical and chemical characteristics to be designed. However, the exhaustive measurement of all these systems is impractical, thus requiring the use of a predictive model for their study. In this work, the predictive capability of the conductor-like screening model for real solvents (COSMO-RS), a model based on unimolecular quantum chemistry calculations, was evaluated for the prediction water activity coefficient at infinite dilution, gamma(infinity)(w), in several classes of ILs. A critical evaluation of the experimental and predicted data using COSMO-RS was carried out. The global average relative deviation was found to be 27.2%, indicating that the model presents a satisfactory prediction ability to estimate gamma(infinity)(w) in a broad range of ILs. The results also showed that the basicity of the ILs anions plays an important role in their interaction with water, and it considerably determines the enthalpic behavior of the binary mixtures composed by Its and water. Concerning the cation effect, it is possible to state that generally gamma(infinity)(w) increases with the cation size, but it is shown that the cation-anion interaction strength is also important and is strongly correlated to the anion ability to interact with water. The results here reported are relevant in the understanding of ILs-water interactions and the impact of the various structural features of its on the gamma(infinity)(w) as these allow the development of guidelines for the choice of the most suitable lLs with enhanced interaction with water.

Effect of the cation on the interactions between alkyl methyl imidazolium chloride ionic liquids and water

A systematic study of the interactions between water and alkyl methyl imidazolium chloride ionic liquids at 298.2 K, based on activity coefficients estimated from water activity measurements in the entire solubility range, is presented. The results show that the activity coefficients of water in the studied ILs are controlled by the hydrophilicity of the cation and the cation-anion interaction. To achieve a deeper understanding on the interactions between water and the ILs, COSMO-RS and FTIR spectroscopy were also applied. COSMO-RS was used to predict the activity coefficient of water in the studied ionic liquids along with the excess enthalpies, suggesting the formation of complexes between three molecules of water and one IL molecule. On the basis of quantum-chemical calculations, it is found that cation-anion interaction plays an important role upon the ability of the IL anion to interact with water. The changes in the peak positions/band areas of OH vibrational modes of water as a function of IL concentration were investigated, and the impact of the cation on the hydrogen-bonding network of water is identified and discussed.

Analysis of the isomerism effect on the mutual solubilities of bis(trifluoromethylsulfonyl)imide-based ionic liquids with water

The knowledge of the liquid-liquid equilibria (LLE) between ionic liquids (ILs) and water is of utmost importance for environmental monitoring, process design and optimization. Therefore, in this work, the mutual solubilities with water, for the ILs combining the 1-methylimidazolium, [C(1)im](+); 1-ethylimidazolium, [C(2)im](+); 1-ethyl-3-propylimidazolium, [C(2)C(3)im](+); and 1-butyl-2,3-dimethylimidazolium, [C(4)C(1)C(1)im](+) cations with the bis(trifluoromethylsulfonyl)imide anion, were determined and compared with the isomers of the symmetric 1,3-dialkylimidazolium bis(trifluoromethylsulfonyl)imide ([C(n)C(n)im][NTf2], with n=1-3) and of the asymmetric 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C(n)C(1)im][NTf2], with n = 2-5) series of ILs. The results obtained provide a broad picture of the impact of the IL cation structural isomerism, including the number of alkyl side chains at the cation, on the water-IL mutual solubilities. Despite the hydrophobic behaviour associated to the [NTf2](-) anion, the results show a significant solubility of water in the IL-rich phase, while the solubility of ILs in the water-rich phase is much lower. The thermodynamic properties of solution indicate that the solubility of ILs in water is entropically driven and highly influenced by the cation size. Using the results obtained here in addition to literature data, a correlation between the solubility of [NTf2]-based ILs in water and their molar volume, for a large range of cations, is proposed. The COnductor like Screening MOdel for Real Solvents (COSMO-RS) was also used to estimate the LLE of the investigated systems and proved to be a useful predictive tool for the a priori screening of ILs aiming at finding suitable candidates before extensive experimental measurements.