Search

U bioinformatici se često javlja potreba za pretraživanjem velikih nizova (DNA i proteinskih sljedova) različitim podnizovima. Kako bi se taj problem riješio u razumnom vremenu, potrebno je koristiti efikasne strukture indeksiranja teksta, kao što su sufiksno stablo i sufiksno polje, koje se mogu izgraditi u linearnom vremenu. Sufiksno polje samo po sebi ima neke nedostatke u odnosu na sufiksno stablo pa se zato često proširuje i nadograđuje. Algoritam gSAIS nadogradnja je popularnog SAIS algoritma za izgradnju sufiksnog polja koja omogućuje izgradnju sufiksnog polja nad kolekcijom nizova. In bioinformatics there is often need to search large strings (DNA and protein sequences) with different substrings. In order to solve this problem in reasonable time, it is necessary to use efficient text indexing structures, such as suffix trees and suffix arrays, which can be built in linear time. The suffix array itself has some disadvantages compared to the suffix tree and is often expanded and upgraded. The gSAIS algorithm is an upgrade of the popular SAIS suffix array construction algorithm that allows the construction of a suffix array over a collection of strings.

Previous studies have shown that excessive salt intake is strongly associated with high blood pressure (HT), vascular dysfunction, and the overall risk of cardiovascular diseases. The aim of this study was to evaluate Sarcocornia effectiveness as a salt substitute, addressing its effect on cardiovascular function in healthy young individuals. Thirty healthy participants, aged 18 to 26 years, were randomized into two groups: the control group (CG) and the intervention group (IG). The IG used Sarcocornia powder as a salt substitute for cooking, and the CG used regular salt, during a period of 1 month. A baseline evaluation was performed before the participants started the intervention phase, and was repeated after a 30-day intervention period. Each evaluation included blood pressure (BP) measurement, carotid-femoral pulse wave velocity (PWV), and carotid pulse wave analysis (PWA), and blood samples were also collected for analysis. Sodium excretion was measured at baseline and after intervention through spot urine collection and analysis, a method suitable for this population but with known limitations. Baseline parameters were similar between groups and were within the normal range. Sodium excretion remained unchanged in the two evaluations in the CG, but significantly decreased after intervention in the IG. The reduction in sodium excretion in the IG was followed by a significant reduction in brachial and aortic systolic (SBP) and diastolic blood pressure (DBP), and also in PWV. No significant changes were observed in the CG in terms of cardiovascular parameters. This preliminary study conveys positive results in favor of Sarcocornia as a dietary substitute for regular salt, providing added evidence of the negative cardiovascular effects of high salt intake in young and healthy adults. info:eu-repo/semantics/publishedVersion

The article analyzes the transformations experienced by a group of communities in the central highlands within the framework of the agrarian reform and the creation of agricultural societies of social interest (SAIS) in the Mantaro valley. It attempts to show that the processes attributed to the changes brought about by the agrarian reform can only be understood with a broader understanding of the processes experienced by the peasant communities in the Mantaro valley. The communal trajectories before, during and after the reform help to understand the processes triggered by the reform and in particular the fate and evolution of the SAIS. Rather than considering associative agriculture as a promoter of technological development in the central highlands, which was cut short by internal contradictions and the actions of Sendero Luminoso, as proposed in previous studies, the idea is to show that the trajectories of the SAIS correspond to the processes that existed before the reform, marked by tensions between the communities and the haciendas, and also between the communities themselves. The article shows, based on the communities that are members of the Cahuide and the Túpac Amaru SAIS –the largest associative enterprises created by the agrarian reform– two different trajectories after the agrarian reform: the first, towards the dissolution of the enterprise and the distribution of its lands, and the second, towards continuity, partial dismemberment and survival in the midst of the crisis. El artículo analiza las transformaciones experimentadas por un grupo de comunidades de la sierra central en el marco de la reforma agraria y la creación de sociedades agrícolas de interés social (SAIS) en el valle del Mantaro. Trata de mostrar que los procesos atribuidos a los cambios propiciados por la reforma agraria solo pueden entenderse mediante una comprensión más amplia de los procesos experimentados por las comunidades campesinas en el valle del Mantaro. Las trayectorias comunales antes, durante y después de la reforma ayudan a comprender los procesos desencadenados con la reforma y en particular el destino y evolución de las SAIS. Más que considerar al agro asociativo como promotor de un desarrollo tecnológico en la sierra central, truncado por las contradicciones internas y el accionar de Sendero Luminoso como proponen estudios previos, se intenta demostrar que las trayectorias de las SAIS corresponden a procesos preexistentes a la reforma, marcados por tensiones entre las comunidades y las haciendas, y también entre las mismas comunidades. El artículo señala, a partir de las comunidades socias de las SAIS Cahuide y Túpac Amaru –las más grandes empresas asociativas creadas por la reforma agraria– dos trayectorias distintas después de la reforma agraria: la primera, hacia la disolución de la empresa y el reparto de sus tierras y la segunda, hacia la continuidad, el desmembramiento parcial y la sobrevivencia en medio de la crisis.

Background Varying results after surgery in patients with subacromial pain syndrome (SAPS) have raised the question on whether there is a subgroup of patients that can benefit from surgery. Therefore, we aimed to identify preoperative and peroperative factors associated with a favorable patient-reported outcome after arthroscopic bursectomy in patients with SAPS. Methods Patients with chronic SAPS who underwent arthroscopic bursectomy after failed conservative management were included (n = 94). Patients were evaluated at the baseline, and 2 weeks, 8 weeks, 6 months, and 1 year after surgery. The primary outcome was the Western Ontario Rotator Cuff index (WORC) score one year after surgery. The secondary outcome measure was a visual analog scale for pain. Mixed model analyses were used to identify prognostic factors. Results The mean WORC (mean difference 39%, 95% confidence interval (CI) 32.8–45.3, P < .001) and visual analog scale pain scores (mean difference 41 mm points, 95% CI 3.37–4.88, P < .001) significantly improved one year after surgery. Nineteen patients (20%) developed a postoperative frozen shoulder. A longer duration of preoperative complaints and the peroperative identification of degenerative glenoid cartilage were associated with significantly worse WORC scores, with −0.086% per month (95% CI −0.156 to −0.016, P = .016) and −20% (95% CI −39.4 to −1.26, P = .037), respectively. Conclusion We identified demographic and clinical factors that predict the course after arthroscopic subacromial bursectomy. We found that arthroscopic bursectomy is less effective in patients with SAPS with a degenerative shoulder. This finding suggests that an improved treatment effect of arthroscopic subacromial bursectomy can be expected in patients with chronic SAPS if intra-articular pathologies such as glenohumeral osteoarthritis are sufficiently excluded.

O cimento de aluminato de cálcio (CAC) é comumente utilizado em meios mais agressivos para as argamassas, pois este cimento é conhecido por ser mais resistente nestas condições quando comparado com o cimento Portland (OPC). Desta forma, o CAC é muito utilizado na formulação de argamassas de junta, uma vez que estas encontram-se mais expostas a ambientes agressivos. Neste estudo, pretendeu-se avaliar a resistência química de uma argamassa de junta constituída por CAC e tripolifosfato de sódio (TPF−Na), considerando que a sua combinação previne a expansão descontrolada durante a imersão em água. Para este efeito, mergulharam-se 5 provetes em diferentes soluções aquosas de ácidos, inorgânicos e orgânicos, durante 35 dias. Especificamente, testou-se o efeito dos ácidos clorídrico, fosfórico, acético, láctico e cítrico. Inicialmente prepararam-se soluções com pH 3,5 e, posteriormente, prepararam-se soluções com pH 2,3 para três dos ácidos, de forma a verificar a influência do pH e, consequentemente, da concentração do ácido, na degradação dos provetes. Todas as soluções foram renovadas ao longo dos 35 dias e realizadas medições de massa e de volume a todos os provetes. Os resultados obtidos permitiram verificar que apenas há degradação dos provetes que se encontravam nas soluções dos ácidos acético e láctico com pH 2,3. Após os 35 dias realizaram-se testes de resistência à compressão aos provetes, tendo-se verificado que os provetes mergulhados em soluções de ácidos apresentam maiores resistências, entre 36 e 54 MPa, quando comparados com o provete padrão, que apresenta uma resistência de 34,76 MPa. Além destes ensaios de resistência, as amostras foram analisadas por termogravimetria acoplada com calorimetria diferencial de varrimento (TG−DSC), difração de raios X (XRD) e espectrometria de infravermelho com transformada de Fourier (FT−IR). A análise por TG−DSC foi realizada para verificar quais as fases do cimento após imersão nas soluções de ácidos, comparando assim com o provete padrão. Com esta comparação verificou-se a existência da fase C-A-P-H em todos os provetes. No entanto, a fase AH3, que resulta do consumo de C3AH6 pelo ataque ácido, só se revelou nos provetes após imersão. De seguida, a análise por XRD visava verificar a presença dos sais, o que não foi possível devido à sua baixa concentração, mas permitiu a identificação das fases CA e CA2. Por último, a espectrometria de FT−IR foi utilizada com a finalidade de avaliar a presença dos sais nas suspensões guardadas ao 14º dia de imersão. Apesar dos resultados terem sido inconclusivos, esta análise permitiu identificar a presença de formiato de cálcio lixiviado da argamassa, assim como, detetar algumas diferenças nas suspensões nomeadamente a pH mais baixo, em que o anião parece estar exclusivamente sob a forma de ião acetato. Calcium aluminate cement (CAC) is commonly used in aggressive media for mortars and is very well known to be more resistant to those conditions when compared with Portland cement (OPC). Thus, CAC is widely used in the formulation of joint mortars, as these are more exposed to aggressive environments. The purpose of this study was to assess the chemical resistance of a joint mortar, that is constituted by CAC and sodium tripolyphosphate (TPF−Na), since this combination prevents the uncontrolled expansion that occurs when the mortar is immersed in water. In order to do this, five specimens were immersed in different acid solutions for a period of 35 days, using both inorganic and organic acids. Specifically, hydrochloric, phosphoric, acetic, lactic and citric acids have been used. Initially acid solutions were prepared with a pH of 3,5 and then for three of the acids, new solutions were prepared with a pH of 2,3 to verify the pH influence and, consequently that of the acid concentration on specimens degradation. For a period of 35 days the solutions were renewed daily and the mass and volume were measured. The results obtained showed that specimens degradation only occurred for those that were immersed in acetic and lactic acid with pH of 2,3. After the 35 day period, the specimens were submitted to compression tests and it was possible to verify that specimens immersed in acid solutions showed better resistances, between 36 and 54 MPa, when compared with ones that weren’t immersed, which presented a resistance of 34,76 MPa. In addition to these tests, the specimens were analysed by thermogravimetry coupled with differential scanning calorimetry (TG−DSC), X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FT−IR). The first one was used to check the differences between the phases present in the immersed and non immersed specimens. With this, it was possible to verify the presence of the C-A-P-H phase in all specimens. However, the AH3 phase is only present in the specimens that have been immerse, due to the consumption of the C3AH6 phase associated with the acid attack. Then, XRD was used aiming at detecting the presence of salts on specimens pores which proved impossible. Yet, the results obtained allowed the identification of the CA and CA2 phases. Finally, FT−IR spectroscopy was used to investigate the presence of salts in suspensions collected on the 14𝑡ℎ day of immersion. Although, the results were inconclusive, it was possible to identify the presence of calcium formiate leached from the mortar. In addition, these spectra revealed some differences between the acetic acid with pH of 3,5 and 2,3, suggesting that the anion is totally in the form of acetate ion at lower pH. Mestrado em Engenharia Química

Dissertação (mestrado)—Universidade de Brasília, Departamento de Botânica, Programa de Pós-Graduação em Botânica, 2016. No Brasil, o feijão-caupi é considerado uma das espécies alimentares mais cultivadas no Norte e Nordeste. Constitui um dos mais importantes componentes da dieta alimentar proteica e energética das populações rurais dessas regiões, é citada como fonte de folatos uma vitamina pertencente ao grupo vitaminas hidrossolúveis do complexo B9. As moléculas de folatos são formadas por três grupos funcionais: pterina, ácido para-aminobenzoico (pABA) e de um a oito resíduos de gluatamato. Em plantas, a primeira reação de produção de folatos é catalisada pela ação da gch1, que fornece instruções para a produção da enzima GTP ciclohidrolase 1, esta enzima está envolvida na primeira etapa da produção de folatos em plantas, produzindo a pterina, enquanto o precursor de pABA é sintetizado no cloroplasto. O objetivo do presente trabalho foi a quantificação do teor de folatos em 50 genótipos de feijão-caupi [Vigna unguiculata (L.) Walp.], disponibilizados pelo banco de germoplasma da Embrapa Meio-Norte (Piauí, Brasil), International Institute of Tropical Agriculture (IITA) (Oyo State, Nigéria) e Ahmadu Bello University (Zária, Nigéria). Além disso, estudou-se a correlação dos teores de folatos e os níveis de expressão do gene Vugch1, que codifica para a GTP ciclohidrolase 1, enzima considerada chave na rota de síntese de pterinas, um precursor de folatos. Os genótipos foram plantados em casa de vegetação e as sementes imaturas foram coletadas com 10, 15, 20 e 25 dias após a antese. O maior nível de expressão de Vugch1 foi observado em sementes coletadas 20 dias após a antese. Com as análises realizadas em sementes maduras constatou-se que houve uma variação no teor de folatos entre 177 a 780 μg/100g (Pingo de Ouro e Yarwaja, respectivamente) nos genótipos estudados, valores estes bem acima dos encontrados na literatura para o feijão-caupi. Confirmou-se a correlação entre a expressão do gene Vugch1 e a variação no teor de folatos. Com esses resultados, existe a possibilidade de avaliar os genótipos mais adequados para utilização de programas de melhoramento genético com variedades de feijão-caupi que possuam maior concentração no teor de folato. Espécies silvestres têm sido exploradas como fonte de alelos de tolerância para o melhoramento genético vegetal de várias culturas. O parental silvestre do amendoim, Arachis duranensis, é um genótipo que apresenta alta adaptabilidade ao déficit hídrico e foi utilizado em um ensaio de dry drown para sequenciamento do transcriptoma. A análise in silico e a validação por RT-qPCR de genes diferencialmente expressos auxiliaram na identificação de genes candidatos associados à resposta a seca. Dentre eles, uma proteína LEA mostrou-se positivamente regulada mediante a esse estresse. Sabe-se que proteínas LEA se comportam como chaperonas e são encontradas em abundância em tecidos sob dessecação, diante disso, o objetivo desse trabalho foi caracterizar, clonar e introduzir esse gene via transgenia em planta modelo (Arabidopsis thaliana) para compreender os efeitos da sua superexpressão. O gene foi inserido em plantas de A. thaliana, ecotipo Columbia 0, utilizando o método de floral dip e os eventos em homozigose (geração T3) foram testados. As linhagens foram plantadas em placas de meio MS com 150 mM de NaCl e 200 mM de manitol, separadamente, além de outro grupo que foi plantado em meio MS e colocado em temperaturas extremas (-18°C por uma hora e 37°C por oito horas). Foram calculadas as taxas de sobrevivência e o teor de açúcares solúveis totais de cada amostra/ensaio. O teste de seca também foi feito, onde a irrigação foi suspensa por 15 dias e foram feitas análises de área foliar, teor relativo de água e coexpressão de genes relacionados à tolerância a seca. Nos ensaios com NaCl e manitol não houveram diferenças entre as linhagens e as plantas não transformadas, além de ter sido observado desenvolvimento reduzido das plantas. Nos ensaios com temperaturas extremas as linhagens mantiveram seus teores de açúcares iguais ao controle enquanto as não-transformadas (NT) aumentaram seu teor de açúcares solúveis totais apenas no tratamento de calor e sem diferença significativa na taxa de sobrevivência entre as linhagens e NT. No ensaio com seca houve maior desenvolvimento da área foliar em algumas linhagens quando comparadas às plantas NT. Na análise de teor relativo de água as linhagens mostraram maiores teores relativos de água quando comparado à NT, sob condição de rega controlada e após 15 dias sem irrigação, sendo uma linhagem com maior teor significativo. Esse evento foi selecionado para a análise de expressão gênica de três genes coexpressos com a Dehidrina. Houve aumento da expressão dos três genes em diferentes situações, tanto pelo fato da planta superexpressar a AdDHN quanto pela indução da seca. Os resultados sugerem que esse gene possa conferir uma melhor resposta aos estresses abióticos. In Brazil, the cowpea is considered one of the most cultivated food species in the North and Northeast. It is one of the most important components of protein and energy diet of rural populations in these regions, is cited as a source of folate a vitamin belonging to the watersoluble vitamins group B9 complex. Folate molecules consist of three functional groups: pterin, para-aminobenzoic acid (pABA) and one to eight residues of gluatamate. In plants, the first folate production is catalyzed by the action of gch1, which provides instructions for the production of the enzyme GTP cyclohydrolase 1, the enzyme is involved in the first step of folate production in plants producing pterin as the precursor pABA is synthesized in the chloroplast. The aim of this study was to quantify the folate content in 50 cultivars of cowpea [Vigna unguiculata (L.) Walp.] provided by the germplasm bank of Embrapa Meio Norte (Piauí, Brazil), International Institute of Tropical Agriculture (IITA) (Oyo State, Nigeria) and Ahmadu Bello University (Zaria, Nigeria). In addition, the correlation of folate content and the expression of the gene Vugch1 was studied. Vugch1 codes for GTP cyclohydrolase 1, a key enzyme for the pterins pathway. The cultivars were planted in the greenhouse and the immature seeds were harvested 10, 15, 20 and 25 days after anthesis. The highest expression level of Vugch1 gene was observed 20 days after anthesis. It was ibserved a variation in the folate content in mature seeds ranging from 177 to 780 μg/100g (Pingo de Ouro and Yarwaja respectively). It was confirmed the correlation between the expression of the Vugch1 gene and folate content. With these results, it is possible to perform appropriate genotype crosses in order to generate new elite varieties with high folate content.

O presente trabalho se reveste do estudo de sais formados “in situ” em uma lagoa salina, localizada no Pantanal, na sub-regiao da Nhecolândia. O objetivo foi caracterizar os sais coletados nas bordas de uma salina, fornecendo dados que auxiliem no entendimento a respeito do ambiente quimico/geoquimico de formacao desses sais. O ambiente de formacao dos sais e caracterizado pelo elevado pH (< 9) e pela alta salinidade (40.000 µS.cm-1), condicoes que favorecem a precipitacao e desenvolvimento dos sais. Os sais foram estudados quanto a sua morfologia e composicao quimica. As morfologias mais frequentes sao os habitos lamelar, fibroso e formato alongado. Quanto a composicao quimica se destaca como predominante a trona (Na3H(CO3)2.2H2O). Em relacao ao seu modo de ocorrencia, os sais ocorrem aglomerados, os cristais se apresentam aglutinados, formados sobre e ao redor dos graos de quartzo, utilizando sua estrutura como zona de nucleacao.

Pharmaceutical cocrystals have emerged over the past several decades as an alternative path for synthesizing stable and/or improved crystalline forms of active pharmaceutical ingredients. In this contribution, we developed a reproducible cocrystallization path for the supramolecular synthesis of four new pharmaceutical cocrystal forms of fluconazole (FLZ), an antifungal multifunctional drug: fluconazole–fumaric acid monohydrate (1:1:1), fluconazole–malic acid (1:1), fluconazole–dipicolinic acid (1:1), and fluconazole–adipic acid (1:1). All the new cocrystals were characterized by powder/single-crystal X-ray diffraction, Raman, Fourier transform infrared spectroscopy, differential scanning calorimetry/thermogravimetric analysis, and hot-stage polarized optical microscopy, and their water solubility was determined. Structurally, although the coformers were different, the same strong O–H···N hydrogen bond between the FLZ molecule and the coformers was observed. The aqueous solubility studies revealed that al...

Fluconazole (FLZ) is one of the most used antifungal drugs worldwide and has been the focus of various investigations with the aim of enhancing its biomedical application. Most of the new solid forms achieved for this drug were determined by powder X-ray diffraction, and a few reports on polymorphs, solvates, cocrystals, and one salt–cocrystal by single-crystal X-ray diffraction (SCXRD) are available. By considering that FLZ is a very weak base (pKa = 1.76, when protonated), salt formation with this drug is expected with the use of very strong organic acids, in order to dislocate the proton from the acid to the FLZ. To the best of our knowledge, only one organic salt of FLZ with picric acid (pKa = 0.38) and one salt–cocrystal (maleate–maleic, pKa1 = 1.92) were reported by SCXRD until now. Having in mind all the advantages that pharmaceutical salts have in drug delivery, in this work we depict the methodology and techniques employed to synthesize a new salt of FLZ using oxalic acid (pKa1 = 1.23). The screening process was initially monitored using Raman spectroscopy, while further characterization by X-ray diffraction (powder and single crystal) and thermal analysis (DSC and TG) was performed to confirm the new salt fluconazolium oxalate (1 : 1). Finally, salt equilibrium solubility studies confirmed an improvement, about 7-fold, when compared to the commercialized active pharmaceutical ingredient (polymorph II). In addition, this is the first reported GRAS (generally regarded as safe) salt of the antifungal drug fluconazole.

Mantaci et al. [TCS 2007] defined the \(\mathrm {eBWT}\) to extend the definition of the \(\mathrm {BWT}\) to a collection of strings. However, since this introduction, it has been used more generally to describe any \(\mathrm {BWT}\) of a collection of strings, and the fundamental property of the original definition (i.e., the independence from the input order) is frequently disregarded. In this paper, we propose a simple linear-time algorithm for the construction of the original \(\mathrm {eBWT}\), which does not require the preprocessing of Bannai et al. [CPM 2021]. As a byproduct, we obtain the first linear-time algorithm for computing the \(\mathrm {BWT}\) of a single string that uses neither an end-of-string symbol nor Lyndon rotations. We combine our new \(\mathrm {eBWT}\) construction with a variation of prefix-free parsing to allow for scalable construction of the \(\mathrm {eBWT}\). We evaluate our algorithm (pfpebwt) on sets of human chromosomes 19, Salmonella, and SARS-CoV2 genomes, and demonstrate that it is the fastest method for all collections, with a maximum speedup of 7.6\(\times \) on the second best method. The peak memory is at most 2\(\times \) larger than the second best method. Comparing with methods that are also, as our algorithm, able to report suffix array samples, we obtain a 57.1\(\times \) improvement in peak memory. The source code is publicly available at https://github.com/davidecenzato/PFP-eBWT.

The article analyzes the transformations experienced by a group of communities in the central highlands within the framework of the agrarian reform and the creation of agricultural societies of social interest (SAIS) in the Mantaro valley. It attempts to show that the processes attributed to the changes brought about by the agrarian reform can only be understood with a broader understanding of the processes experienced by the peasant communities in the Mantaro valley. The communal trajectories before, during and after the reform help to understand the processes triggered by the reform and in particular the fate and evolution of the SAIS. Rather than considering associative agriculture as a promoter of technological development in the central highlands, which was cut short by internal contradictions and the actions of Sendero Luminoso, as proposed in previous studies, the idea is to show that the trajectories of the SAIS correspond to the processes that existed before the reform, marked by tensions between the communities and the haciendas, and also between the communities themselves. The article shows, based on the communities that are members of the Cahuide and the Túpac Amaru SAIS –the largest associative enterprises created by the agrarian reform– two different trajectories after the agrarian reform: the first, towards the dissolution of the enterprise and the distribution of its lands, and the second, towards continuity, partial dismemberment and survival in the midst of the crisis. El artículo analiza las transformaciones experimentadas por un grupo de comunidades de la sierra central en el marco de la reforma agraria y la creación de sociedades agrícolas de interés social (SAIS) en el valle del Mantaro. Trata de mostrar que los procesos atribuidos a los cambios propiciados por la reforma agraria solo pueden entenderse mediante una comprensión más amplia de los procesos experimentados por las comunidades campesinas en el valle del Mantaro. Las trayectorias comunales antes, durante y después de la reforma ayudan a comprender los procesos desencadenados con la reforma y en particular el destino y evolución de las SAIS. Más que considerar al agro asociativo como promotor de un desarrollo tecnológico en la sierra central, truncado por las contradicciones internas y el accionar de Sendero Luminoso como proponen estudios previos, se intenta demostrar que las trayectorias de las SAIS corresponden a procesos preexistentes a la reforma, marcados por tensiones entre las comunidades y las haciendas, y también entre las mismas comunidades. El artículo señala, a partir de las comunidades socias de las SAIS Cahuide y Túpac Amaru –las más grandes empresas asociativas creadas por la reforma agraria– dos trayectorias distintas después de la reforma agraria: la primera, hacia la disolución de la empresa y el reparto de sus tierras y la segunda, hacia la continuidad, el desmembramiento parcial y la sobrevivencia en medio de la crisis.

The article traces the trajectories followed by associative enterprises after the agrarian reform in Puno. It analyzes the changes in the structure of the land in light of the processes of agrarian restructuring and the formation of new peasant communities. The central argument is that the agrarian reform implemented by the Velasco government had peculiarities that should be incorporated in the reading of it as a process with regional variations. Likewise, it is argued, based on the analysis and history of two large associative companiesapparatus did not make an adequate reading of the different land tenure logics of the peasant livestock families, nor of the pressure for water and land resources of the surrounding communities. The struggle for land, which arose from the expectations of thousands of communal families and from a distribution considered unequal, is one of the central axes of this text. From this perspective, the reform, more than an event that lasted from 1969 to 1975, was a process that was superimposed on previous, longer-term dynamics, which was inserted in diverse territories and in ongoing social microprocesses with which it overlapped, generating tensions and conflicts in the two following decades. In the case studied, this implied the reconfiguration of the South Andean space and the consolidation of hundreds of communities with a land tenure regime within it. El artículo traza las trayectorias que siguieron las empresas asociativas en Puno después de la reforma agraria. Analiza los cambios en la estructura de la tierra a la luz de los procesos de reestructuración agraria y de la formación de nuevas comunidades campesinas. El planteamiento central es que la reforma agraria implementada por el gobierno de Velasco tuvo particularidades que deben ser incorporadas en la lectura de esta como un proceso con variaciones regionales. Asimismo,se sostiene, a partir del análisis y trayectoria de dos grandes empresas asociativas –Picotani y Kunurana–, que el aparato del gobierno velasquista no realizó una lectura adecuada de las distintas lógicas de tenencia de la tierra de las familias campesinas ganaderas, ni de la presión de las comunidades colindantes por los recursos de agua y tierra. La lucha por la tierra, surgida por las expectativas de miles de familias comuneras y por una distribución considerada desigual, es uno de los ejes centrales de este texto. Desde esa perspectiva, la reforma agraria, más que un evento que duró unos años (1969-1975), fue un proceso que se superpuso a dinámicas previas de más largo plazo y se insertó en territorios diversos y en microprocesos sociales en curso con los cuales se traslapó, lo que generó tensiones y conflictos en las siguientes dos décadas. En el caso que se ha estudiado, ello implicó la reconfiguración del espacio surandino y la consolidación de cientos de comunidades con un régimen de tenencia de la tierra parcelario en su interior.&nbsp

Chitosan (CS) and carrageenan (CRG), two marine-derived polymers, were selected as matrix materials for the preparation of nanoparticles by polyelectrolyte complexation. The effect of polymer concentration in the production of CS/CRG nanoparticles and on the characteristics of the final product (size and zeta potential) was studied. Furthermore, an experimental design was used to evaluate the effect of adding three different salts, NaCl, CaCl2 and Na2SO4, to the formulations. From the obtained results, different mathematical models were established, allowing to have a tool to predict the characteristics of the nanoparticles according to the production parameters. Overall, the results permitted drawing some conclusions, including the fact that the concentration of CRG in the formulations did not impact the size of the nanoparticles and the observation that the inclusion of Na2SO4, even at a concentration of 0.006M, which is considered low, results in the production of micro-sized carriers instead of nanoparticles. For NaCl and CaCl2 it was observed that there was an inversion in the pattern of evolution of NP size with variation of CS concentration when the salt concentration increased. Nevertheless, there was a significant lack of fit of the model regarding the size, which indicates that an improvement is necessary to better fit the data. Regarding the zeta potential, and as expected, a general increase was seen with the increase of CS concentration, although some deviations to this normal behaviour were observed that deserve further testing. The concentrations used for these salts might not have been enough to produce a noticeable effect in the particles’ characteristics. As the concentration of the salts were not liable to increase, since they were at the highest concentration possible that guaranteed polymer solubility, other salts could be tested in the future. O quitosano (CS) e a carragenina (CRG), dois polímeros marinhos, foram selecionados como materiais de matriz para a preparação de nanopartículas por complexação polieletrolítica. Foi estudado o efeito da concentração dos polímeros na produção de nanopartículas de CS/CRG e nas características do produto final (tamanho e potencial zeta). Para além disso, foi usado um desenho experimental para avaliar o efeito da adição de três sais diferentes, NaCl, CaCl2 e Na2SO4, nas formulações. A partir dos resultados obtidos, foram estabelecidos diferentes modelos matemáticos, permitindo ter uma ferramenta para prever as características das nanopartículas de acordo com os parâmetros de produção. De uma maneira geral, os resultados permitiram tirar algumas conclusões, incluindo o facto de que a concentração de CRG nas formulações não teve impacto no tamanho das nanopartículas. Também se verificou que a inclusão de Na2SO4, mesmo à concentração de 0,006M, considerada baixa, resulta na produção de transportadores na escala micrométrica em vez de nanopartículas. Para o NaCl e o CaCl2 observou-se que, com o aumento da concentração de sal, houve uma inversão no padrão de evolução do tamanho das nanopartículas em função da variação da concentração de CS. No entanto, houve uma falta de ajuste significativa do modelo em relação ao tamanho, o que indica que é necessária uma melhoria do ajuste dos dados. Em relação ao potencial zeta, e como esperado, observou-se um aumento geral com o aumento da concentração de CS, embora tenham sido observados alguns desvios a este comportamento normal que requerem mais estudo. As concentrações usadas para os sais utilizados podem não ter sido suficientes para produzir um efeito percetível nas características das partículas. Como a concentração dos sais não pode ser aumentada, visto ser a concentração máxima possível que garantia a solubilidade dos polímeros, outros sais poderiam ser testados no futuro

Orientadores: José Vicente Hallak Dangelo, Roger Josef Zemp Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química Resumo: O licor negro é uma solução aquosa, subproduto do processo de cozimento da madeira e constituído de matéria orgânica (lignina, polissacarídeos, ácidos carboxílicos e extrativos) e matéria inorgânica (residual dos reagentes químicos utilizados na etapa de cozimento da madeira). Este licor é encaminhado para a unidade de recuperação para ser concentrado em evaporadores de múltiplos efeitos e posteriormente, ser encaminhado para a caldeira de recuperação com os objetivos de: recuperar e reciclar os reagentes químicos utilizados no cozimento da madeira, gerar vapor para a produção de energia elétrica e incinerar todos os resíduos não desejáveis. Quando o licor negro é encaminhado do digestor para os evaporadores, apresenta em média 17% de sólidos totais. Na medida que este licor vai sendo concentrado e começa a aproximar-se de 50% de sólidos totais, a solução torna-se saturado e o limite de solubilidade de alguns sais inorgânicos é atingido, ocasionando, inicialmente, a cristalização e nucleação e finalmente a precipitação destes sais. Estes precipitados podem ocasionar a formação de depósitos e incrustações nas paredes dos evaporadores o que leva ao entupimento das tubulações necessitando de constantes paradas na produção para limpeza. Em função deste grande problema que as empresas de papel e celulose vêm enfrentando, no Brasil e em outros países, torna-se imprescindível a realização de um estudo detalhado e minucioso da forma como estes sais solúveis comportam-se, desde o momento na qual são alimentados nos evaporadores, até o momento na qual ocorre a precipitação destes sais. Dentre os sais solúveis presentes no licor negro, os mais importantes são o sulfato de sódio (Na2SO4) e carbonato de sódio (Na2CO3). Então, estes foram os sais escolhidos para o estudo de seus comportamentos na unidade de evaporação. Para tanto, várias etapas serão utilizadas para a conclusão da pesquisa. O presente trabalho tem por objetivo investigar os sólidos críticos do licor negro e o processo de solubilidade do sulfato de sódio e carbonato de sódio em licor negro de eucalipto Abstract: Black liquor is an aqueous solution, a byproduct of the wood cooking process and composed of organic matter (lignin, polysaccharides, carboxylic and extractive acids) and inorganic matter (residual of the chemical reagents used in the cooking step of the wood). This liquor is conveyed to the recovery unit to be concentrated in multi-effect evaporators and then sent to the recovery boiler for the purpose of: recovering and recycling the chemical reagents used in cooking the wood, generating steam for the production of and incinerate all unwanted waste. When the black liquor is sent from the digester to the evaporators, it presents on average 17% of total solids. As this liquor is being concentrated and begins to approach 50% of total solids, the solution becomes saturated and the solubility limit of some inorganic salts is reached, initially causing crystallization and nucleation, and finally precipitation of these salts. These precipitates can cause the formation of deposits and incrustations in the walls of the evaporators which leads to the clogging of the pipes necessitating constant stops in the production for cleaning. Due to this great problem that paper and pulp companies are facing, in Brazil and in other countries, it is essential to carry out a detailed and detailed study of the way these soluble salts behave, from the moment they are fed in the evaporators, until the moment in which the precipitation of these salts occurs. Among the soluble salts present in the black liquor, the most important are sodium sulfate (Na2SO4) and sodium carbonate (Na2CO3). So these were the salts chosen for the study of their behaviors in the evaporation unit. To do so, several steps will be used to complete the search. The present work aims to investigate the critical solids of black liquor and the solubility process of sodium sulfate and sodium carbonate in black eucalyptus liquor Doutorado Engenharia Química Doutora em Engenharia Química CNPQ 140520/2010-4

Aqueous biphasic systems (ABS) are biocompatible systems applied in the extraction of biomolecules. Despite the biocompatibility of polymers and, particularly polyethylene glycol (PEG), to form ABS, their limitation in terms of phase separation is recognized. A new approach was recently proposed based on the use of ionic liquids (ILs) as adjuvants in ABS, enlarging the polarity range of these systems. Up to now, the effects of ILs in PEG-salt ABS have been poorly described. To overcome this limitation, the phase diagrams of imidazolium-based ILs acting as adjuvants in ABS based in PEG with potassium salt buffers (pH = 7), that is potassium citrate (C6H5K3O7/C6H8O7) and potassium phosphate (K2HPO4/KH2PO4) buffers, are herein addressed. Imidazolium-based ILs were focused in this work, since they have been applied on the purification of several biomolecules with success, even as adjuvants or electrolytes. The phase diagrams were mapped out for PEG/salt ABS without adjuvants. In this work, systems composed of PEG (1000, 1500, 2000, 3350, 4000, 6000, and 8000) with potassium phosphate buffer and PEG (2000, 6000, 10 000, and 20 000) with potassium citrate buffer were tested. Moreover, the presence of 5 wt % of imidazolium-based ILs (varying the anion moiety) for the system PEG 1500 with potassium phosphate buffer was also investigated. Imidazolium-based ILs with different anions were tested to investigate a large range of polarities attributed to the adjuvant. Moreover, the effect of the adjuvant content (5, 10, and 20 wt %) in the PEG 2000 with potassium citrate buffer system was studied for two distinct ILs, namely [C4mim][CF3SO3] and [C4mim][(CH3O)2PO2], with lower and higher energy of intramolecular hydrogen bond, EHB, respectively, a parameter representing the ions' hydration. A correlation between the anion moiety of imidazolium-based IL and the ability to form two phases was observed, being this related to the ILs' anion EHB value. The concentration of the adjuvant confirmed the effects of enhancing or decreasing the ability to form two phases for ILs with lower and higher EHB value, respectively. published

The article traces the trajectories followed by associative enterprises after the agrarian reform in Puno. It analyzes the changes in the structure of the land in light of the processes of agrarian restructuring and the formation of new peasant communities. The central argument is that the agrarian reform implemented by the Velasco government had peculiarities that should be incorporated in the reading of it as a process with regional variations. Likewise, it is argued, based on the analysis and history of two large associative companies apparatus did not make an adequate reading of the different land tenure logics of the peasant livestock families, nor of the pressure for water and land resources of the surrounding communities. The struggle for land, which arose from the expectations of thousands of communal families and from a distribution considered unequal, is one of the central axes of this text. From this perspective, the reform, more than an event that lasted from 1969 to 1975, was a process that was superimposed on previous, longer-term dynamics, which was inserted in diverse territories and in ongoing social microprocesses with which it overlapped, generating tensions and conflicts in the two following decades. In the case studied, this implied the reconfiguration of the South Andean space and the consolidation of hundreds of communities with a land tenure regime within it. El artículo traza las trayectorias que siguieron las empresas asociativas en Puno después de la reforma agraria. Analiza los cambios en la estructura de la tierra a la luz de los procesos de reestructuración agraria y de la formación de nuevas comunidades campesinas. El planteamiento central es que la reforma agraria implementada por el gobierno de Velasco tuvo particularidades que deben ser incorporadas en la lectura de esta como un proceso con variaciones regionales. Asimismo, se sostiene, a partir del análisis y trayectoria de dos grandes empresas asociativas –Picotani y Kunurana–, que el aparato del gobierno velasquista no realizó una lectura adecuada de las distintas lógicas de tenencia de la tierra de las familias campesinas ganaderas, ni de la presión de las comunidades colindantes por los recursos de agua y tierra. La lucha por la tierra, surgida por las expectativas de miles de familias comuneras y por una distribución considerada desigual, es uno de los ejes centrales de este texto. Desde esa perspectiva, la reforma agraria, más que un evento que duró unos años (1969-1975), fue un proceso que se superpuso a dinámicas previas de más largo plazo y se insertó en territorios diversos y en microprocesos sociales en curso con los cuales se traslapó, lo que generó tensiones y conflictos en las siguientes dos décadas. En el caso que se ha estudiado, ello implicó la reconfiguración del espacio surandino y la consolidación de cientos de comunidades con un régimen de tenencia de la tierra parcelario en su interior.

In order to seek for new compounds with antitumor activity, our research group is focused on copper complexes with mixed ligands. This work presents the synthesis and characterization of eight compounds with general formula [Cu(iminodiacetate)(diimine)(H2O)x], with x = 0 or 1, and their cytotoxic activities against tumor cells. The chosen diimine ligands were: 2,2-dipyridil-amine (bam), 2,2-bipyridine (bipy), 4,4-dimethyl-2,2-bipyridine (dmb), 1,10-phenanthroline (phen), 4-methyl-1,10-phenanthroline (4met-phen), 5-nitro-1,10-phenanthroline (5nitro-phen), neocuproine (neo) and bathophenanthroline (batho). Compounds were characterized in solid state using FT-IR, TGA, DSC and single crystal X-ray diffraction analyses by which five new crystal structures were determined. Common features of the coordination scheme include fac-NO + O isomerism of the iminodiacetate (ida) ligand, except for the complex with neo where the ida presents mer-NO2 isomerism. The diimine ligand completes the equatorial plane for the facial isomers, with different degrees of distortion in the octahedral or square-based pyramid geometry depending on the diimine ligand, whereas the neo is perpendicular to the equatorial plane in the latter. Studies in solution, using EPR, UV–Vis spectroscopy and conductimetry, showed that the copper coordination observed in solid state is retained except for the batho complex. DNA interaction studies evidenced that the complexes bind to this biomolecule, inducing different conformational changes. Biological experiments evidenced that all complexes induce cell death in the cell line MDA-MD-231 (metastasic breast cancer line). [Cu(ida)(neo)] and [Cu(ida)(batho)] presented the highest activity. Taken all these data together we propose that [Cu(ida)(neo)] and [Cu(ida)(batho)] are good candidates for further studies in vitro and in vivo.

Mechanochemistry synthesis was applied to the supramolecular synthesis and green scale-up production of a 1:1 drug–drug cocrystal involving the antimetabolite prodrug 5-Fluorocytosine (5-FC) and the tuberculostatic drug Isoniazid (INH), namely, 5FC-INH. Crystalline material, also obtained by traditional slow evaporation methods, was analyzed by single-crystal X-ray diffraction (XRD). The crystal packing is stabilized by a classical N–H···N hydrogen-bond interaction between the amine moiety of 5-FC and the INH pyridine nitrogen. IR and Raman data provided spectroscopic evidence about the hydrogen atom positions, thereby confirming the neutral nature of the cocrystal. Furthermore, 5FC-INH codrug was also evaluated by a range of analytical techniques such as powder XRD and thermal (thermogravimetric analysis, differential scanning calorimetry, hot stage microscopy) analyses. A physical stability study was performed in high relative humidity conditions to verify possible 5-FC solid-state hydration and/or INH ...

Hexafluorosilicate salts of the antidepressant drugs Paroxetine (PRX) and Fluoxetine (FLX), [PRX]2SiF6 and [FLX]2SiF6⋅H2O, are investigated herein by SCXRD, Hirshfeld surface analysis, and Infrared spectroscopy. By their crystal structures, it is possible to observe, for the first time, at least at the best of our knowledge, the formation of a supramolecular architecture of the [SiF6]2− anion with protonated secondary amine groups. The [PRX]2SiF6 crystallizes in the P21 space group and the [FLX]2SiF6⋅H2O in the P21/c, as a hydrate racemate. While two conformers are present in the asymmetric unit of [PRX]2SiF6, two enantiomers enclose the one of [FLX]2SiF6⋅H2O. Analysis of the crystal packing show that N HF Si (1.94–2.42 Ǻ), C HF Si (2.36–2.62 A), and C Hπ interactions are the main contributors toward the supramolecular architectures in these salts.

Solid solutions could represent a viable alternative to better understand and control structure–property relationships of drugs, in order to optimize their properties for practical applications. Lamivudine (3TC) and emtricitabine (FTC) are nucleoside analogue reverse transcriptase inhibitor antiretroviral drugs, which have similar molecular structures, differing by a single fluorine atom, which is only present in the FTC molecule. Due to these similarities in structure and molecular resemblances, lamivudine and emtricitabine are good candidates for producing a solid solution with physicochemical properties controlled by the stoichiometry. Following this hypothesis, the formation of a nonconventional solid solution was verified, whose crystalline structure is not defined by any of the individual constituents but by the one of the lamivudine hydrate with emtricitabine as a solute. The crystalline structures of two members of the solid solution were determined showing a nonuniform distribution of the solute ...

The structure of choline salts containing the anions acetate, [Chol][Ac], and dihydrogen phosphate, [Chol][DHP], were investigated by infrared, Raman, and inelastic neutron scattering (INS). The chosen systems allow for the comparison of structural effects related to the bond acceptor characteristic of [Ac] and the simultaneous acceptor and donor characteristics of [DHP] in forming hydrogen bonds (H-bond) in salts of [Chol], which is itself prone to forming H-bonds. Different computational tools were used for the analysis of different spectral ranges. The calculation of the low-frequency range of Raman and INS spectra of the crystalline phases at low-temperatures by solid state DFPT (density functional perturbation theory) unveils the coupling between vibrations of the H-bonds and intramolecular modes. Changes observed in the spectral pattern of lattice and [DHP] modes upon heating crystalline [Chol][DHP] are analogous to the ferroelectric–paraelectric phase transition known in the potassium salt of [DHP]. The fingerprint region of the vibrational spectra provides information concerning the [Chol] conformation in the solid phase (gauche in [Chol][Ac] and anti in [Chol][DHP]) and in aqueous solution. DFT calculations of ionic pairs and ionic clusters unveil the interplay between [Chol] conformation and the [DHP] ability to form H-bonded dimers of anions. The high-frequency spectral range and the structures driven by H-bonds are discussed using classical molecular dynamics (MD) simulations. The MD simulations of aqueous solutions highlight the strong anion-cation H-bond in [Chol][Ac], in contrast to the strong anion–anion H-bond in [Chol][DHP] due to occurrence of dimers and larger clusters of [DHP].