Nanostructured lipid carriers as vehicles for the delivery of poorly water-soluble drugs

186 p.

Characterization of water-soluble organic compounds in bioaerosols by liquid chromatography and fluorescence spectroscopy

In the last decades, the effects of the air pollution have been increasing, especially in the case of the human health diseases. In order to overcome this problem, scientists have been studying the components of the air. As a part of water-soluble organic compounds, amino acids are present in the atmospheric environment as components of diverse living organisms which can be responsible for spreading diseases through the air. Liquid chromatography is one technique capable of distinguish the different amino acids from each other. In this work, aiming at separating the amino acids found in the aerosols samples collected in Aveiro, the ability of four columns (Mixed-Mode WAX-1, Mixed-Mode HILIC-1, Luna HILIC and Luna C18) to separate four amino acids (aspartic acid, lysine, glycine and tryptophan) and the way the interaction of the stationary phases of the columns with the analytes is influenced by organic solvent concentration and presence/concentration of the buffer, are being assessed. In the Mixed-Mode WAX-1 column, the chromatograms of the distinct amino acids revealed the separation was not efficient, since the retention times were very similar. In the case of lysine, in the elution with 80% (V/V) MeOH, the peaks appeared during the volume void. In the Mixed-Mode HILIC-1 column, the variation of the organic solvent concentration did not affect the elution of the four studied amino acids. Considering the Luna HILIC column, the retention times of the amino acids were too close to each other to ensure a separation among each other. Lastly, the Luna C18 column revealed to be useful to separate amino acids in a gradient mode, being the variation of the mobile phase composition in the organic solvent concentration (ACN). Luna C18 was the column used to separate the amino acids in the real samples and the mobile phase had acidified water and ACN. The gradient consisted in the following program: 0 – 2 min: 5% (V/V) ACN, 2 – 8 min: 5 – 2 % (V/V) ACN, 8 – 16 min: 2% (V/V) ACN, 16 – 20 min: 2 – 20 % (V/V) ACN, 20 – 35 min: 20 – 35 % (V/V) ACN. The aerosols samples were collected by using three passive samplers placed in two different locations in Aveiro and each sampler had two filters - one faced up and the other faced down. After the sampling, the water-soluble organic compounds was extracted by dissolution in ultra-pure water, sonication bath and filtration. The resulting filtered solutions were diluted in acidified water for the chromatographic separation. The results from liquid chromatography revealed the presence of the amino acids, although it was not possible to identify each one of them individually. The chromatograms and the fluorescence spectra showed the existence of some patterns: the samples that correspond to the up filters had more intense peaks and signals, revealing that the up filters collected more organic matter.

Transport in the blood of an anti-tumor water-soluble rutheniun cyclopentadienyl complex: a fluorescence study on albumin binding

Dissertação de mestrado, Qualidade em Análises, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2014

Development of water-soluble polyanionic carbosilane dendrimers as novel and highly potent topical anti-HIV-2 microbicides

This is the author’s version of a work that was accepted for publication in Nanoscale.

Sintesi e proprietà fotovoltaiche di politiofeni water- soluble

Nell’ottica di una limitazione dello sfruttamento di fonti fossili, della diminuzione delle emissioni di gas serra e dell’introduzione, nel mercato energetico, di dispositivi fotovoltaici organici (OPVs) che permettano di sfruttare l’energia solare conferendo leggerezza e flessibilità alle celle fotovoltaiche, è stato sintetizzato un nuovo polialchiltiofene contenente unità elettron-donatrici e accettrici in catena principale, da testare come strato fotoattivo all’interno di un dispositivo OPV. In particolare, a partire da 1,6-dibromoesano e 3-bromotiofene, è stato preparato 4,7-bis(3-(6-bromoesil)tiofen-2-il)-2,1,3-benzotiadiazolo mediante reazione di cross-coupling di Suzuki con l’estere pinacolico dell'acido 2,1,3-benzotiadiazolo-4,7-bis(boronico) e, successivamente, polimerizzato via metodo ossidativo con FeCl3. Il polimero ottenuto, poli(4,7-bis(3-(6-bromoesil)tiofen-2-il)-2,1,3-benzotiadiazolo), è stato caratterizzato mediante analisi TGA, DSC, FTIR-ATR, GPC, 1H-NMR e UV-Vis. Verrà, in seguito, post-funzionalizzato con tributilfosfina per ottenere un polimero ionico solubile in acqua o in solventi polari, al fine di evitare l’impiego di solventi aromatici o clorurati durante la deposizione del film polimerico all’interno della cella fotovoltaica.

Sintesi e caratterizzazione di materiali polimerici water-soluble per applicazioni nel campo del fotovoltaico organico

The need to use renewable energy sources, due to the massive production of pollution for the energy production, has led to the development of new technologies for the use of solar energy. The purpose of this thesis project is to synthesize and characterize new thiophene-based polymeric materials processable in water, a green solvent, for the construction of organic solar cells, promising and versatile devices used for the production of electric energy. For this, a highly regioregular polymer was synthesized through GRIM polymerization (Grignard Metathesis Polymerization) on which a study was performed to identify the optimal reaction time.

Studio e sintesi di politiofeni water-soluble contenenti gruppi elettron donatori e accettori in catena principale

Il progressivo esaurimento delle risorse fossili e l’incremento delle problematiche ambientali legate al rilascio di gas serra contribuiscono alla ricerca e all’utilizzo di fonti energetiche alternative. In questo scenario, i dispositivi fotovoltaici organici (OPVs) rappresentano uno dei modi più affascinanti e promettenti per trasformare l’energia solare, una riserva energetica potenzialmente inesauribile, a costo nullo e non inquinante, in energia elettrica. Materiali organici utilizzabili in questi dispositivi sono i polimeri π-coniugati. In quest’ottica, il lavoro è stato focalizzato sulla preparazione di due nuovi polimeri: il primo, contenente unità elettron-donatrici e accettrici in catena principale, ottenuto via polimerizzazione ossidativa in presenza di FeCl3 e successivamente post-funzionalizzato con tributilfosfina per renderlo ionico e idrosolubile; il secondo, a base di politiofene non ionico ma polare, avente funzionalità eteree nelle catene laterali, preparato sfruttando il metodo GRIM. Questi materiali sono stati caratterizzati mediante analisi spettroscopiche e verranno successivamente testati all’interno di celle solari fotovoltaiche organiche aventi configurazione SMOSCs (il primo) e BHJ (il secondo).

Nutritional reserves of Vochysiaceae seeds: chemical diversity and potential economic uses

Contents of proteins, carbohydrates and oil of seeds of 57 individuals of Vochysiaceae, involving one species of Callisthene, six of Qualea, one of Salvertia and eight of Vochysia were determined. The main nutritional reserves of Vochysiaceae seeds are proteins (20% in average) and oils (21. 6%). Mean of carbohydrate contents was 5. 8%. Callisthene showed the lowest protein content (16. 9%), while Q. cordata was the species with the highest content (30% in average). The contents of ethanol soluble carbohydrates were much higher than those of water soluble carbohydrates. Oil contents lay above 20% for most species (30. 4% in V. pygmaea and V. pyramidalis seeds). The predominant fatty acids are lauric (Q. grandiflora), oleic (Qualea and Salvertia) or acids with longer carbon chains (Salvertia and a group of Vochysia species). The distribution of Vochysiaceae fatty acids suggests for seeds of some species an exploitation as food sources (predominance of oleic acid), for other species an alternative to cocoa butter (high contents or predominance of stearic acid) or the production of lubricants, surfactants, detergents, cosmetics and plastic (predominance of acids with C20 or C22 chains) or biodiesel (predominance of monounsaturated acids). The possibility of exploitation of Vochysiaceae products in a cultivation regimen and in extractive reserves is discussed.

Efeitos do teor de carboidratos solúveis sobre as características da silagem de cana-de-açúcar

Objetivou-se quantificar na cana-de-açúcar o teor de carboidratos solúveis (CHOs) que anula a produção de etanol e avaliar os efeitos desses carboidratos sobre o valor nutritivo e outras características fermentativas da silagem de cana-de-açúcar. Utilizou-se o delineamento inteiramente casualizado com três tratamentos, cada um com quatro repetições. Os tratamentos consistiram da retirada total do caldo da cana-de-açúcar, por meio de prensagem, e de sua reconstituição (0, 50 ou 100%) à cana. No nível de 50% de reconstituição, o caldo foi adicionado à cana juntamente com 50% de água e, no nível 0%, adicionou-se 100% de água à cana. A restituição resultou em concentrações de 41,6; 34,0 e 23,0% de carboidratos solúveis na matéria seca (MS). O material foi ensilado em 12 silos experimentais confeccionados a partir de baldes plásticos. A abertura dos silos foi realizada 85 dias após a ensilagem, quando foram determinados os teores dos ácidos orgânicos e a composição química das silagens. A retirada de carboidratos solúveis da cana-de-açúcar teve efeito linear decrescente sobre os teores de matéria seca, o teor de carboidratos solúveis e a digestibilidade in vitro da matéria seca (DIVMS) das silagens, no entanto, ocasionou aumento dos teores de fibra detergente ácido (FDA), fibra detergente neutro (FDN) e lignina. Observou-se efeito linear decrescente da retirada dos carboidratos solúveis sobre os teores de etanol e ácidos lático e butírico e as perdas de matéria seca das silagens. Não se observaram efeitos de tratamentos sobre os dados de estabilidade aeróbia. A produção de etanol seria nula se a cana-de-açúcar contivesse apenas 12,4% de CHOs com base na matéria seca (MS).

Evaluation of corn cultivars harvested at two cutting heights for ensilage

The objective of this study was to evaluate the agronomic characteristics, bromatological-chemical composition and digestibility of 11 corn cultivars (Zea mays) harvested at two cutting heights. Cultivars D 766, D 657, D 1000, P 3021, P 3041, C 805, C 333, AG 5011, FO 01, CO 9621 and BR 205 were evaluated when they were harvested 5 cm above ground (low) and 5 cm below the insertion of the first ear (high). The experiment was designed as random blocks, with three replicates, arranged in an 11 x 2 factorial scheme. Cultivars presented similar productions of forage dry matter and grains. Percentages of stalk, leaf, straw, cob and kernel fractions were different among cultivars, as well as dry matter content of the whole plant at harvest. Considering the whole plant, only the contents of gross energy, nitrogen in neutral detergent fiber, and in vitro neutral and acid detergent fiber digestibility did not differ among cultivars. Increase on the cutting height improved forage quality due to the reduction of stalk and leaf fractions and contents of cell wall constituents.

Microbial and biochemical soil quality indicators and their potential for differentiating areas under contrasting agricultural management regimes

The aim of this study was to examine interrelationships between functional biochemical and microbial indicators of soil quality, and their suitability to differentiate areas under contrasting agricultural management regimes. The study included five 0.8 ha areas on a sandy-loam soil which had received contrasting fertility and cropping regimes over a 5 year period. These were organically managed vegetable, vegetable -cereal and arable rotations, an organically managed grass clover ley, and a conventional cereal rotation. The organic areas had been converted from conventional cereal production 5 years prior to the start of the study. All of the biochemical analyses, including light fraction organic matter (LFOM) C and N, labile organic N (LON), dissolved organic N and water-soluble carbohydrates showed significant differences between the areas, although the nature of the relationships between the areas varied between the different parameters, and were not related to differences in total soil organic matter content. The clearest differences were seen in LFOM C and N and LON, which were higher in the organic arable area relative to the other areas. In the case of the biological parameters, there were differences between the areas for biomass-N, ATP, chitin content, and the ratios of ATP: biomass and basal respiration: biomass. For these parameters, the precise relationships between the areas varied. However, relative to the conventionally managed area, areas under organic management generally had lower biomass-N and higher ATP contents. Arbuscular mycorrhizal fungus colonization potential was extremely low in the conventional area relative to the organic areas. Further, metabolic diversity and microbial community level physiological profiles, determined by analysis of microbial community metabolism using Biolog GN plates and the activities of eight key nutrient cycling enzymes, grouped the organic areas together, but separated them from the conventional area. We conclude that microbial parameters are more effective and consistent indicators of management induced changes to soil quality than biochemical parameters, and that a variety of biochemical and microbial analyses should be used when considering the impact of management on soil quality. (C) 2004 Elsevier Ltd. All rights reserved.

Whole crop cereals 2. Prediction of apparent digestibility and energy value from in vitro digestion techniques and near infrared reflectance spectroscopy and of chemical composition by near infrared reflectance spectroscopy

Samples of whole crop wheat (WCW, n = 134) and whole crop barley (WCB, n = 16) were collected from commercial farms in the UK over a 2-year period (2003/2004 and 2004/2005). Near infrared reflectance spectroscopy (NIRS) was compared with laboratory and in vitro digestibility measures to predict digestible organic matter in the dry matter (DOMD) and metabolisable energy (ME) contents measured in vivo using sheep. Spectral models using the mean spectra of two scans were compared with those using individual spectra (duplicate spectra). Overall NIRS accurately predicted the concentration of chemical components in whole crop cereals apart from crude protein. ammonia-nitrogen, water-soluble carbohydrates, fermentation acids and solubility values. In addition. the spectral models had higher prediction power for in vivo DOMD and ME than chemical components or in vitro digestion methods. Overall there Was a benefit from the use of duplicate spectra rather than mean spectra and this was especially so for predicting in vivo DOMD and ME where the sample population size was smaller. The spectral models derived deal equally well with WCW and WCB and Would he of considerable practical value allowing rapid determination of nutritive value of these forages before their use in diets of productive animals. (C) 2008 Elsevier B.V. All rights reserved.

Prediction of metabolisable energy concentrations of fresh cut grass using digestibility data measured with non-pregnant non-lactating cows

Pasture-based ruminant production systems are common in certain areas of the world, but energy evaluation in grazing cattle is performed with equations developed, in their majority, with sheep or cattle fed total mixed rations. The aim of the current study was to develop predictions of metabolisable energy (ME) concentrations in fresh-cut grass offered to non-pregnant non-lactating cows at maintenance energy level, which may be more suitable for grazing cattle. Data were collected from three digestibility trials performed over consecutive grazing seasons. In order to cover a range of commercial conditions and data availability in pasture-based systems, thirty-eight equations for the prediction of energy concentrations and ratios were developed. An internal validation was performed for all equations and also for existing predictions of grass ME. Prediction error for ME using nutrient digestibility was lowest when gross energy (GE) or organic matter digestibilities were used as sole predictors, while the addition of grass nutrient contents reduced the difference between predicted and actual values, and explained more variation. Addition of N, GE and diethyl ether extract (EE) contents improved accuracy when digestible organic matter in DM was the primary predictor. When digestible energy was the primary explanatory variable, prediction error was relatively low, but addition of water-soluble carbohydrates, EE and acid-detergent fibre contents of grass decreased prediction error. Equations developed in the current study showed lower prediction errors when compared with those of existing equations, and may thus allow for an improved prediction of ME in practice, which is critical for the sustainability of pasture-based systems.

Prediction of nutrient digestibility and energy concentrations in fresh grass using nutrient composition

Improved nutrient utilization efficiency is strongly related to enhanced economic performance and reduced environmental footprint of dairy farms. Pasture-based systems are widely used for dairy production in certain areas of the world, but prediction equations of fresh grass nutritive value (nutrient digestibility and energy concentrations) are limited. Equations to predict digestible energy (DE) and metabolizable energy (ME) used for grazing cattle have been either developed with cattle fed conserved forage and concentrate diets or sheep fed previously frozen grass, and the majority of them require measurements less commonly available to producers, such as nutrient digestibility. The aim of the present study was therefore to develop prediction equations more suitable to grazing cattle for nutrient digestibility and energy concentrations, which are routinely available at farm level by using grass nutrient contents as predictors. A study with 33 nonpregnant, nonlactating cows fed solely fresh-cut grass at maintenance energy level for 50 wk was carried out over 3 consecutive grazing seasons. Freshly harvested grass of 3 cuts (primary growth and first and second regrowth), 9 fertilizer input levels, and contrasting stage of maturity (3 to 9 wk after harvest) was used, thus ensuring a wide representation of nutritional quality. As a result, a large variation existed in digestibility of dry matter (0.642-0.900) and digestible organic matter in dry matter (0.636-0.851) and in concentrations of DE (11.8-16.7 MJ/kg of dry matter) and ME (9.0-14.1 MJ/kg of dry matter). Nutrient digestibilities and DE and ME concentrations were negatively related to grass neutral detergent fiber (NDF) and acid detergent fiber (ADF) contents but positively related to nitrogen (N), gross energy, and ether extract (EE) contents. For each predicted variable (nutrient digestibilities or energy concentrations), different combinations of predictors (grass chemical composition) were found to be significant and increase the explained variation. For example, relatively higher R(2) values were found for prediction of N digestibility using N and EE as predictors; gross-energy digestibility using EE, NDF, ADF, and ash; NDF, ADF, and organic matter digestibilities using N, water-soluble carbohydrates, EE, and NDF; digestible organic matter in dry matter using water-soluble carbohydrates, EE, NDF, and ADF; DE concentration using gross energy, EE, NDF, ADF, and ash; and ME concentration using N, EE, ADF, and ash. Equations presented may allow a relatively quick and easy prediction of grass quality and, hence, better grazing utilization on commercial and research farms, where nutrient composition falls within the range assessed in the current study.

Evaluating nitrogen utilization efficiency of nonpregnant dry cows offered solely fresh cut grass at maintenance levels

The present study aimed to identify key parameters influencing N utilization and develop prediction equations for manure N output (MN), feces N output (FN), and urine N output (UN). Data were obtained under a series of digestibility trials with nonpregnant dry cows fed fresh grass at maintenance level. Grass was cut from 8 different ryegrass swards measured from early to late maturity in 2007 and 2008 (2 primary growth, 3 first regrowth, and 3 second regrowth) and from 2 primary growth early maturity swards in 2009. Each grass was offered to a group of 4 cows and 2 groups were used in each of the 8 swards in 2007 and 2008 for daily measurements over 6 wk; the first group (first 3 wk) and the second group (last 3 wk) assessed early and late maturity grass, respectively. Average values of continuous 3-d data of N intake (NI) and output for individual cows ( = 464) and grass nutrient contents ( = 116) were used in the statistical analysis. Grass N content was positively related to GE and ME contents but negatively related to grass water-soluble carbohydrates (WSC), NDF, and ADF contents ( < 0.01), indicating that accounting for nutrient interrelations is a crucial aspect of N mitigation. Significantly greater ratios of UN:FN, UN:MN, and UN:NI were found with increased grass WSC contents and ratios of N:WSC, N:digestible OM in total DM (DOMD), and N:ME ( < 0.01). Greater NI, animal BW, and grass N contents and lower grass WSC, NDF, ADF, DOMD, and ME concentrations were significantly associated with greater MN, FN, and UN ( < 0.05). The present study highlighted that using grass lower in N and greater in fermentable energy in animals fed solely fresh grass at maintenance level can improve N utilization, reduce N outputs, and shift part of N excretion toward feces rather than urine. These outcomes are highly desirable in mitigation strategies to reduce nitrous oxide emissions from livestock. Equations predicting N output from BW and grass N content explained a similar amount of variability as using NI and grass chemical composition (excluding DOMD and ME), implying that parameters easily measurable in practice could be used for estimating N outputs. In a research environment, where grass DOMD and ME are likely to be available, their use to predict N outputs is highly recommended because they strongly improved of the equations in the current study.