This study investigated efficacy of an online, preventive intervention program, Children of Divorce-Coping with Divorce (CoD-CoD; Boring, 2011). It extends previous findings to a sample of eight youth from high-conflict families who recently initiated legal divorce proceedings. CoD-CoD is a cognitive-behavioral intervention that targets coping efficacy, coping strategies, and divorce-related cognitive appraisals. A multiple-baseline single case experimental design evaluated change in daily use of active and avoidant coping strategies and corresponding coping efficacy ratings. Individual patterns of change were inspected for the program’s putative mediator variables and overall mental health functioning. Results indicate that daily coping efficacy ratings increased for four participants and decreased for the three participants who reported the highest levels of exposure to interparental conflict. The majority of participants increased use of at least one type of active coping strategy and half decreased use of at least one type of avoidant coping strategy. There were no observed patterns of systematic change in divorce-related cognitive appraisals and changes in mental health functioning were mixed. An exploratory analysis found that youth were classified as "high-risk" on a psychometrically-sound risk index in 100% of cases with documentation of two or more conflict-indicative legal events in the family court file. The study findings are consistent with previous evidence of a moderated program effect on coping efficacy, although positive effects on youth-reported mental health functioning were not replicated. Findings are discussed within the context of a high-conflict sample with temporal proximity to the legal divorce and in light of study limitations. Research directions toward effectively connecting at-risk youth with evidence-based prevention services are detailed.

Orientador: Francisco Maugeri Filho / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-04T01:27:34Z (GMT). No. of bitstreams: 1 Santos_TihanyMoritaAnterodos_D.pdf: 818442 bytes, checksum: c034c03d154eadb3c1ed625f0144e680 (MD5) Previous issue date: 2004 / Resumo: O xilitol é um açúcar-álcool com ampla utilização na indústria alimentícia, porém mesmo sendo numerosos os estudos sobre a sua produção a partir da fermentação de hidrolisados hemicelulósicos, poucos são os trabalhos que tratam da sua separação e purificação. O objetivo principal deste trabalho é, portanto, desenvolver uma metodologia de separação do xilitol dos compostos remanescentes no meio fermentado obtido por fermentação do hidrolisado de bagaço de cana-de-açúcar por Candida guilliermondii. Inicialmente, ensaios conduzidos com as zeólitas Na86X, Baylith 415 e Baylith WE 894 em diferentes formas catiônicas permitiram constatar a maior eficácia das zeólitas NaWE e BaWE na adsorção do xilitol e posteriormente, o uso de colunas de leito fixo empacotadas com estas duas zeólitas em diferentes granulometrias, a 30 e 50 ºC, revelou que a separação do xilitol foi superior com o uso da zeólita BaWE com partículas de 53-125 µm a 50 ºC. Estas condições foram empregadas na determinação da constante de equilíbrio deste composto usando a resposta a pulsos cromatográficos, sendo o valor obtido igual a 1,03. Os efeitos da temperatura, da velocidade superficial e da razão volume de pulso/volume de leito (Vp/Vl) sobre a separação do xilitol foram investigados através de análise estatística de experimentos delineados por um planejamento fatorial 23, que revelou que a condição mais favorável para separar o xilitol envolve o uso de temperatura de 80 ºC, velocidade superficial de 0,5 cm.min-1 e Vp/Vl igual a 0,2. O emprego de etanol e acetona em diferentes concentrações como eluentes permitiu concluir, após avaliação das eficiências obtidas e do custo dos mesmos, que o etanol a 30 % é o eluente mais adequado para ser utilizado na separação do xilitol. Após a determinação dos parâmetros de separação em meio sintético, iniciaram-se os testes com meio fermentado, obtido da fermentação de hidrolisado de bagaço de cana-de-açúcar com Candida guilliermondii. Dentre as metodologias empregadas na destoxificação deste meio, o uso de resinas de troca iônica foi o mais eficiente, permitindo obter maiores parâmetros fermentativos. A avaliação da separação do xilitol obtido por fermentação foi realizada variando-se o número de colunas e o volume do pulso e os melhores resultados foram obtidos utilizando-se 2 e 3 colunas de zeólita BaWE alimentadas com volume de pulso igual a 8 % do volume do leito. Apesar das eficiências de separação terem sido superiores com 3 colunas, verificou-se que a porcentagem de xilitol nas frações enriquecidas e a quantidade recuperada deste poliol foram somente ligeiramente superiores às obtidas em sistema com 2 colunas (0,5 e 2,1 % superiores, respectivamente). Além deste fato, o sistema de 2 colunas contribuiu para uma eluição mais rápida dos compostos e requereu menor volume de eluente. Estas observações permitiram concluir que dentre os sistemas experimentais avaliados, o composto por 2 colunas de zeólita BaWE com altura total de leito de 89 cm, alimentadas com volume de pulso igual a 8 % do volume do leito, a 80 ºC e 0,5 cm.min-1 conduziu a uma melhor separação do xilitol. Nestas condições obteve-se uma fração com 97,28 % de xilitol, 0,84 % de arabinose, 0,82 % de xilose e 0,54 % de arabitol e eficiências de separação de 3,17 e 2,72 com relação a arabinose e a xilose, respectivamente / Abstract: Xylitol is a sugar alcohol with large utilization in food industry. Nevertheless, although there are numerous studies on its production from the fermentation of hemicellulosic hydrolysates, there are few works dealing with its separation and purification. The principal aim of this work is, therefore, to develop a methodology for xylitol separation from the compounds remaining in the fermented medium, which was obtained by fermentation with Candida guilliermondii in sugar cane bagasse hydrolysate. Initially, assays were conducted with the zeolites Na86X, Baylith 415 and Baylith WE 894 in different cationic forms, which permitted us to observe a higher effectiveness of zeolites NaWE and BaWE in the xylitol adsorption, and later, the use of fixed bed columns packed with these two zeolites in different granulometries, at 30 and 50 ºC, revealed that the xylitol separation was better when 53-125 µm BaWE zeolite particles at 50 ºC were utilized. These conditions were also employed for determining the equilibrium constant of this compound using the chromatographic pulse response technique, the value obtained being equal to 1.03. The effects of temperature, superficial velocity and pulse volume/bed volume ratio (Vp/Vl) on the xylitol separation were investigated by means of statistical analysis of experiments described by a 23 factorial design, which showed that the most favorable conditions for this separation are: temperature of 80 ºC, superficial velocity of 0.5 cm.min-1 and Vp/Vl of 0.2. The use of ethanol and acetone at different concentrations as eluents enabled us to conclude, after an evaluation of their costs and of the efficiencies obtained, that ethanol at 30 % is the most suitable eluent for xylitol separation. After determining the parameters of separation in synthetic medium, tests were performed with fermented medium obtained from fermentation of sugar cane bagasse hydrolysate with Candida guilliermondii. Of the methodologies employed for detoxification of this medium, the use of ion-exchange resins proved the most effective, giving higher fermentative parameters. The separation of xylitol obtained from fermentation was evaluated by varying the number of columns and the pulse volume, the best results being attained with 2 and 3 columns of zeolite BaWE fed with a pulse volume equal to 8 % of bed volume. Although the separation efficiencies were enhanced by using 3 columns, it was observed that the amount of xylitol in the enriched fractions and its recovered amount were only slightly higher than those obtained using 2 columns (0.5 and 2.1 % higher, respectively). In addition, the 2-column system contributed to a more rapid elution of the compounds and required a lower eluent volume. It can therefore be concluded that, of the experimental systems that were evaluated, the one composed of two columns of zeolite BaWE with a bed 89 cm in total height and fed with a pulse volume equal to 8 % of bed volume, at 80 ºC and 0.5cm.min-1, led to a better xylitol separation. Under these conditions, the fraction obtained contained 97.28 % xylitol, 0.84 % arabinose, 0.82 % xylose and 0.54 % arabitol, and the efficiencies of xylitol separation from arabinose and xylose were 3.17 and 2.72 respectively / Doutorado / Engenharia de Alimentos / Doutor em Engenharia de Alimentos

A large portion of research in science and engineering, as well as in business, concerns one similar problem: how to make things "better”? Once properly modeled (although usually a highly nontrivial task), this kind of questions can be approached via a mathematical optimization problem. Optimal solution to a mathematical optimization problem, when interpreted properly, might corresponds to new knowledge, effective methodology or good decisions in corresponding application area. As already proved in many success stories, research in mathematical optimization has a significant impact on numerous aspects of human life. Recently, it was discovered that a large amount of difficult optimization problems can be formulated as copositive programming problems. Famous examples include a large class of quadratic optimization problems as well as many classical combinatorial optimization problems. For some more general optimization problems, copositive programming provides a way to construct tight convex relaxations. Because of this generality, new knowledge of copositive programs has the potential of being uniformly applied to these cases. While it is provably difficult to design efficient algorithms for general copositive programs, we study copositive programming from two standard aspects, its relaxations and its separation problem. With regard to constructing computational tractable convex relaxations for copositive programs, we develop direct constructions of two tensor relaxation hierarchies for the completely positive cone, which is a fundamental geometric object in copositive programming. We show connection of our relaxation hierarchies with known hierarchies. Then we consider the application of these tensor relaxations to the maximum stable set problem. With regard to the separation problem for copositive programming. We first prove some new results in low dimension of 5 x 5 matrices. Then we show how a separation procedure for this low dimensional case can be extended to any symmetric matrices with a certain block structure. Last but not least, we provide another approach to the separation and relaxations for the (generalized) completely positive cone. We prove some generic results, and discuss applications to the completely positive case and another case related to box-constrained quadratic programming. Finally, we conclude the thesis with remarks on some interesting open questions in the field of copositive programming.

This dissertation addresses the rational design of intrinsically microporous solutionprocessable polyimides and ladder polymers for highly permeable and highly selective gas transport in cornerstone applications of membrane-based gas separation – that is, air enrichment, hydrogen recovery and natural gas sweetening. By virtue of rigid and contorted chains that pack inefficiently in the solid state, polymers of intrinsic microporosity (PIMs) have the potential to unite the solution-processability, mechanical flexibility and organic tunability of commercially relevant polymers with the microporosity characteristics of porous crystalline materials. The performance enhancements of PIMs over conventional low-free-volume polymers have been primarily permeability-driven, compromising the selectivity essential to commercial viability. An approach to unite high permeability with high selectivity for performance transcending the state-of-the-art in air and hydrogen separations was demonstrated via a fused-ring integration of a three-dimensional, shape persistent triptycene moiety optimally substituted with short, branched isopropyl chains at the 9,10-bridgeheads into a highly inflexible backbone. The resulting polymers exhibited selectivities (i.e., O2/N2, H2/N2, H2/CH4) similar to or higher than commercial materials matched with permeabilities up to three hundred times higher. However, the intra-chain rigidity central to such conventional PIM-design principles was not a singular solution to suppression of CO2-induced plasticization in CO2/CH4 mixedgas separations. Plasticization diminishes the sieving capacity of the membrane, resulting in costly hydrocarbon losses that have significantly limited the commercialization of new polymers. Unexpectedly, the most permeable and selective PIMs designed for air and hydrogen separations strongly plasticized in 50:50 CO2/CH4 mixtures, enduring up to three-fold increases in mixed-gas CH4 permeability by 30 bar and strong drops in selectivity. Instead, a paradigm shift emphasizing inter-chain rigidity was demonstrated for the PIM-type polyimides via introduction of a flexible diamine functionalized with hydroxyl groups. Intra-chain flexibility may permit short-range coplanarization of backbone segments which facilitates inter-chain interactions likely comprising charge transfer complexes over the N-phenyl imide bond and hydrogen bonding. Relative to commercial cellulose acetate membranes at a representative 10 bar CO2 partial pressure, the resulting polyimide exhibited two-fold increases in mixed-gas CO2/CH4 selectivity (~50) concurrent with nearly 10-fold higher CO2 gas permeability. Similar design principles were drawn for ladder polymers.

Control at the molecular level over porous solid-state materials is of prime importance for fine-tuning the local structures, as well as the resultant properties. Traditional porous solid-state materials such as zeolite and activated carbon are the benchmarks in the current market with vital applications in sorption and heterogeneous catalysis. However, the adjustments of pore size and geometry of those materials, which are essential for the broader aspect of modern prominent applications, remain challenging. Reticular chemistry has emerged as a dominant tool toward the ‘designed syntheses’ of porous crystalline frameworks (e.g. metal-organic frameworks (MOFs)) with a specific pore system. This dissertation illustrates the power of reticular chemistry and its use in the directional assembly of highly coordinated MOF materials, as well as their potential applications such as gas storage, natural gas upgrading, and light hydrocarbon separation. Highly connected minimal edge-transitive derived and related nets, obtained via the deconstruction of nodes of the edge-transitive nets, are suitable blueprints and can potentially be deployed in the future ‘designed syntheses’ of MOFs. The further employment of the conceptual net-coded building units (e.g. highly connected MBBs and edge-transitive SBLs) in the practical reticular synthesis results in the rational design and construction of functional MOF platforms like shp-, alb-, kce-, kex- and eea- MOFs. In addition, the isoreticular synthesis of Al-cea-MOF-2 with functionalized pendant acid moieties inside pore channels in comparison to the parent Al-cea-MOF-1 led to enhanced light hydrocarbons separation performance. Moreover, controlling the molecular defects in Zr-fum-fcu-MOFs resulted in the development of an ultramicroporous adsorbent with an engineered aperture size for the highly efficient separation of butane/iso-butane.

Metal-organic frameworks (MOFs) are porous crystalline materials built by metal clusters coordinated to organic ligands. Synthesis of MOFs has attracted considerable attention in recent decades, owing to its potential for a wide range of applications such as gas separation, dye adsorption, and catalysis, etc. The development of MOF membranes further enhances the potential of this type of material in industrial applications. Membrane fabrication methods, including in-situ growth, seeded secondary growth, interfacial growth, and vapor-phase deposition, have been widely studied. However, most of these methods either require a complicated synthesis procedure or are timeconsuming. Recently, the electrochemical synthesis has emerged as a highly promising approach to fabricate MOF membranes in a scalable manner, because it allows shorter synthesis time, milder synthesis condition, continuous reaction, and crystal self-healing. In this thesis, for the first time, an aqueously cathodic deposition (ACD) approach was developed to fabricate ZIF-8 type of MOF membranes without the addition of any supporting electrolyte or modulator. The fabrication process used 100% water as the sole solvent, and a low-defect density membrane was obtained in only 60 min under room temperature without any pre-synthesis treatment. The membrane exhibited superior performance in C3H6/C3H8 separation with C3H6 permeance of 182 GPU and selectivity of 142, making it sit at the upper bound of permeance versus selectivity graph, outperforming the majority of the published data up to 2019. Notably, this approach used an extremely low current density (0.13 mA cm-2) operated under a facile apparatus setup, enabling an attractive method for environmentally friendly, energy-efficient, and scalable MOF membrane fabrications. This work demonstrates the enormous potential of aqueously electrochemical deposition of the MOF membrane in future research.

The polyolefins production is the largest among all types of plastics given their thermal and chemical stability and low cost, which allows them to be used in a wide variety of products worldwide, including polypropylene (PP) and polyethylene (PE) membranes. However, the small percentage of polyolefins being recycled compared to the enormous amount produced has led to severe environmental pollution issues. In addition, the traditional polyolefin membrane fabrication methods utilize mostly toxic non-renewable solvents such as xylenes at high temperatures, causing further negative environmental impact. The objective of this study is to propose a greener alternative for polyolefins in general and in particular for membrane fabrication. For this, two bio-based solvents (α-pinene and Dlimonene) were proposed to dissolve PP and LDPE, and the resulting films and membrane properties were studied. Hydrophobic PP microporous membranes were obtained by thermally induced phase separation from pristine commercial polymers and plastic waste. They were applied for water-in-toluene emulsion separation. The water rejection was above 95% for membranes fabricated from dope solutions containing 25% pristine PP and 30% waste PP heated at 130°C, suggesting that they could be used in oil spill recovery operations. This work aims to contribute to the implementation of more sustainable practices in the membrane industry.

Cascading Style Sheets (CSS) has become essential to front-end web development for the specification of style. But despite its simple syntax and the theoretical advantages attained through the separation of style from content and behavior, CSS authoring today is regarded as a complex task. As a result, developers are increasingly turning to CSS preprocessor languages and web frameworks to aid in development. However, previous studies show that even highly popular websites which are known to be developed with web frameworks contain CSS code smells such as duplicated rules and hard-coded values. Such code smells have the potential to cause adverse effects on websites and complicate maintenance. It is therefore important to investigate whether web frameworks may be encouraging the introduction of CSS code smells into websites. In this thesis, we investigate the prevalence of CSS code smells in websites built with different web frameworks and attempt to recognize a pattern of CSS behavior in these frameworks. We collect a dataset of several hundred websites produced by each of 19 different frameworks, collect code smells and other metrics present in the CSS code of each website, train a classifier to predict which framework the website was built with, and perform various clustering tasks to gain insight into the correlations between code smells. Our results show that CSS code smells are highly prevalent in websites built with web frameworks, we achieve an accuracy of 39% in correctly classifying the frameworks based on CSS code smells and metrics, and we find interesting correlations between code smells.

No description available.

My dissertation is an investigation into the basic Physics of phase separation fronts. Such phase-separation fronts occur in many practical applications, like the formation of immersion precipitation membranes, Temperature induced phase-separation of polymeric blends, or the formation of steel. Despite the fact that these phenomena are ubiquitous no generally acceptable theory of phase-separation front exists. I believe the reason lies in the complexity of many of these material systems where a large number of physical effects (like phase-separation, crystallization, hydrodynamics, etc) cooperate to generate these structures. As a Physicist, I was driven to develop an understanding of these systems, and we choose to start our investigation with the simplest system that would incorporate a phase-separation front. So we initially limited our study to systems with a purely diffusive dynamics. The phase-separation front is induced by a control-parameter front that is a simple step function advancing with a prescribed velocity. We investigated these systems numerically using a lattice Boltzmann method and also investigated them analytically as much as possible. Starting from a one-dimensional front moving with a constant velocity we then extended the complexity of the systems by increasing the number of dimensions, examining a variable front velocity, and finally by including hydrodynamics.