Highly robust chitosan hydrogels via a fast, simple and biocompatible dual crosslinking-based process

Load-bearing soft tissues such as cartilage, blood vessels and muscles are able to withstand a remarkable compressive stress of several MPa without fracturing. Interestingly, most of these structural tissues are mainly composed of water and in this regard, hydrogels, as highly hydrated 3D-crosslinked polymeric networks, constitute a promising class of materials to repair lesions on these tissues. Although several approaches can be employed to shape the mechanical properties of artificial hydrogels to mimic the ones found on biotissues, critical issues regarding, for instance, their biocompatibility and recoverability after loading are often neglected. Therefore, an innovative hydrogel device made only of chitosan (CHI) was developed for the repair of robust biological tissues. These systems were fabricated through a dual-crosslinking process, comprising a photo- and an ionic-crosslinking step. The obtained CHIbased hydrogels exhibited an outstanding compressive strength of ca. 20 MPa at 95% of strain, which is several orders of magnitude higher than those of the individual components and close to the ones found in native soft tissues. Additionally, both crosslinking processes occur rapidly and under physiological conditions, enabling cellsâ encapsulation as confirmed by high cell survival rates (ca. 80%). Furthermore, in contrast with conventional hydrogels, these networks quickly recover upon unloading and are able to keep their mechanical properties under physiological conditions as result of their non-swell nature.

Removal of ochratoxin A from contaminated white and red wines using oenological fining agents

Mycotoxins are toxic secondary metabolites produced by certain moulds, being ochratoxin A (OTA) one of the most relevant. Its chemical structure is a dihydro-isocoumarin connected at the 7-carboxy group to a molecule of L--phenylalanine via an amide bond. OTA contamination of wines might be a risk to consumer health, thus requiring treatments to achieve acceptable standards for human consumption [1]. According to the Regulation No. 1881/2006 of the European Commission, the maximum limit for OTA in wine is 2 µg/kg [2]. Therefore, the aim of this work was to know the effect of different fining agents on OTA removal, as well as their impact on white and red wine physicochemical characteristics. To evaluate their efficiency, 11 commercial fining agents (mineral, synthetic, animal and vegetable proteins) were used to get new approaches on OTA removal from white and red wines. Trials were performed in wines artificially supplemented (at a final concentration of 10 µg/L) with OTA. The most effective fining agent in removing OTA (80%) from white wine was a commercial formulation that contains gelatine, bentonite and activated carbon. Removals between 10-30% were obtained with potassium caseinate, yeast cell walls and pea protein. With bentonites, carboxymethylcellulose, polyvinylpolypyrrolidone and chitosan no considerable OTA removal was verified. In red wine, removals between 6-19% were obtained with egg albumin, yeast cell walls, pea protein, isinglass, gelatine, polyvinylpolypyrrolidone and chitosan. The most effective fining agents in removing OTA from red wine were an activated carbon (66%) followed again by the commercial formulation (55%), being activated carbon a well-known adsorbent of mycotoxins. These results may provide useful information for winemakers, namely for the selection of the most appropriate oenological product for OTA removal, reducing wine toxicity and simultaneously enhancing food safety and wine quality.

An overview of the brewing process

The first chapter of this book has an introductory character, which discusses the basics of brewing. This includes not only the essential ingredients of beer, but also the steps in the process that transforms the raw materials (grains, hops) into fermented and maturated beer. Special attention is given to the processes involving an organized action of enzymes, which convert the polymeric macromolecules present in malt (such as proteins and polysaccharides) into simple sugars and amino acids; making them available/assimilable for the yeast during fermentation.

Caracterização de materiais plásticos usados na indústria têxtil e de vestuário por FTIR

Dissertação de mestrado em Técnicas de Caracterização e Análises Químicas

Development of a poly(L-Lactic acid) based drug release system

Dissertação de mestrado em Biofísica e Bionanossistemas

Development of active bio-based multilayer systems: encapsulation of cinnamaldehyde and their physicochemical characterization

[Excerpt] In this work, different multilayer structures, using a polyhydroxybutyrate-co-valerate film with a valerate content of 8% (PHBV8) as support, were developed aiming the development of active bio-based multilayer systems. An interlayer based on zein nanofibers with and without cinnamaldehyde were electrospun in the PHBV8 film and three multilayer systems were developed: 1) without an outer layer; 2) using a PHBV8 film as outer layer; and 3) using an alginate-based film as outer layer. Their physico-chemical properties were evaluated through: water vapour and oxygen permeabilities and colour measurements, Fourier Transform Infrared Spectroscopy (FTIR) and thermal analyses. Results showed that the presence of different outer layers affected the water vapour permeability and transparency of the multilayer films. (...)

Activity of carvacrol against Coagulase-negative Staphylococci biofilm related infections

Dissertação de mestrado em Bioengenharia

Electronic tongue: a versatile tool for mineral and fruit-flavored waters recognition

Natural mineral waters (still), effervescent natural mineral waters (sparkling) and aromatized waters with fruit-flavors (still or sparkling) are an emerging market. In this work, the capability of a potentiometric electronic tongue, comprised with lipid polymeric membranes, to quantitatively estimate routinely quality physicochemical parameters (pH and conductivity) as well as to qualitatively classify water samples according to the type of water was evaluated. The study showed that a linear discriminant model, based on 21 sensors selected by the simulated annealing algorithm, could correctly classify 100 % of the water samples (leave-one out cross-validation). This potential was further demonstrated by applying a repeated K-fold cross-validation (guaranteeing that at least 15 % of independent samples were only used for internal-validation) for which 96 % of correct classifications were attained. The satisfactory recognition performance of the E-tongue could be attributed to the pH, conductivity, sugars and organic acids contents of the studied waters, which turned out in significant differences of sweetness perception indexes and total acid flavor. Moreover, the E-tongue combined with multivariate linear regression models, based on sub-sets of sensors selected by the simulated annealing algorithm, could accurately estimate waters pH (25 sensors: R 2 equal to 0.99 and 0.97 for leave-one-out or repeated K-folds cross-validation) and conductivity (23 sensors: R 2 equal to 0.997 and 0.99 for leave-one-out or repeated K-folds cross-validation). So, the overall satisfactory results achieved, allow envisaging a potential future application of electronic tongue devices for bottled water analysis and classification.

Влияние пространственной структуры молекул фталевых кислот на их адсорбционные свойства

წყლის ორთქლთან ადსორბციის მექანიზმის შესახებ ინფორმაციის მისაღებად ტერეფტალმჟავის და მისი იზომერების ორთოფტალმჟავის და იზოფტალმჟავის მოლეკულების აღნაგობა იყო გამოკვლეული.

Обработка углеродных адсорбентов методом механохимической активации с целью воздействия на теплые туманы

თბილ ნისლებზე ზემოქმედების მიზნით დამუშავებული იქნა ტექნოლოგია და მეთოდიკა წვრილდისპერსული ნახშირბადოვანი ადსორბენტის მასალებად მექანოქიმიური აქტივაციის გზით

Thickening of phase change materials (PCM) to avoid segregation

Estudi elaborat a partir d’una estada a Çukurova University, Turquia, al juliol del 2006. L’emmagatzematge d’energia tèrmica ha atret interès en aplicacions tèrmiques com l’aigua calenta, la calefacció i l’aire condicionat. Aquests sistemes són útils per corregir la no coincidència entre la oferta i la demanda d’energia. Principalment hi ha dos tipus de sistemes d’emmagatzematge d’energia tèrmica, emmagatzematge amb calor sensible i amb calor latent. L’emmagatzematge amb calor latent és particularment atractiu degut a la seva habilitat de donar una densitat d’emmagatzematge d’energia més alt i la seva característica d’emmagatzemar calor a una temperatura constant corresponent a la temperatura de transició de fase de la substància emmagatzemadora de calor. Les salts hidratades orgàniques tenen certes avantatges com a materials d’emmagatzematge de calor latent sobre els materials orgànics. En canvi, quan les salts hidratades s’utilitzen com a materials de canvi de fase (PCM) apareixen alguns problemes en les aplicacions d’emmagatzematge de calor latent. Aquests són el subrefredament de les salts hidratades quan es congelen degut a les seves dèbils propietats de nucleació, i la separació de fase que hi apareix degut a una fusió incongruent. En aquest estudi, s’estabilitza sal de Glauber (Na2SO4.10H2O) amb diferents concentracions de poliacrilamida i gelatina per prevenir la fusió incongruent. Per prevenir el subrefredament s’utilitza un agent nucleant amb una estructura cristal•lina semblant a la de la sal de Glauber. La capacitat d’emmagatzematge de calor de les mostres de PCM estabilitzades amb diferents concentracions de gels polimèrics es determinen amb DCS i amb el mètode T-history.

Desenvolupament d'hidrogels superficials que contenen motius d'adhesió cel·lular

Projecte de recerca elaborat a partir d’una estada al Departament d’Enginyeria Química del Massachusetts Institute of Technology entre abril i octubre del 2006. S’ha dissenyat i sintetitzat uns nous films polimèrics, amb aplicacions en l’àmbit de l’enginyeria de teixits, utilitzant la tècnica anomenada iCVD (initiated Chemical Vapor Deposition), prèviament desenvolupada pel grup receptor. Es tracta d’uns hidrogels superficials de gruix controlable, que incorporen un monòmer fluorat, el qual s’havia estudiat extensament en el grup d’origen. Aquest monòmer es caracteritza per reaccionar molt fàcilment amb pèptids, de manera que aquests queden units covalentment a la superfície. Diferents estratègies pel desenvolupament d’aquests copolímers han estat avaluades, tant des del punt de vista purament sintètic com de la pròpia aplicació. Les condicions de polimerització han estat optimitzades i els hidrogels s’han caracteritzat químicament per tècniques espectroscòpiques (FTIR, XPS), i físicament per angle de contacte i el·lipsometria. D’aquesta manera, s’ha estudiat la capacitat dels hidrogels d’absorbir aigua i alhora augmentar el seu gruix, depenent de la quantitat d’agent reticulant introduït i de la incorporació del nou monòmer. A continuació, s’han optimitzat les condicions de reacció d’aquestes superfícies amb pèptids que incorporen una molècula fluorescent, la qual permet detectar fàcilment per microscòpia de fluorescència si la reacció ha tingut lloc. Una vegada la plataforma ha estat posada a punt, s’han iniciat assajos cel·lulars tant amb fibroblasts embriònics de ratolí com amb cèl·lules humanes umbilicals. Els resultats preliminars suggereixen una morfologia diferent de les cèl·lules segons si es cultiven sobre films modificats amb pèptids que promouen l’adhesió cel·lular o sobre les seves seqüències permutades no actives. Però, el més interessant és que també s’han observat certes diferències depenent si els films contenen el component hidrogel o no, fet que suggeriria un paper actiu d’aquests noves superfícies en el comportament cel·lular.

Targeting of secretory IgA to Peyer's patch dendritic and T cells after transport by intestinal M cells.

In addition to being instrumental to the protection of mucosal epithelia, secretory IgA (SIgA) adheres to and is transported by intestinal Peyer's patch (PP) M cells. The possible functional reason for this transport is unknown. We have thus examined in mice the outcome of SIgA delivered from the intestinal lumen to the cells present in the underlying organized mucosa-associated lymphoreticular tissue. We show selective association of SIgA with dendritic cells and CD4(+) T and B lymphocytes recovered from PP in vitro. In vivo, exogenously delivered SIgA is able to enter into multiple PP lining the intestine. In PP, SIgA associates with and is internalized by dendritic cells in the subepithelial dome region, whereas the interaction with CD4(+) T cells is limited to surface binding. Interaction between cells and SIgA is mediated by the IgA moiety and occurs for polymeric and monomeric molecular forms. Thus, although immune exclusion represents the main function of SIgA, transport of the Ab by M cells might promote Ag sampling under neutralizing conditions essential to the homeostasis of mucosal surfaces.

Transfer of ultrasmall iron oxide nanoparticles from human brain-derived endothelial cells to human glioblastoma cells.

Nanoparticles (NPs) are being used or explored for the development of biomedical applications in diagnosis and therapy, including imaging and drug delivery. Therefore, reliable tools are needed to study the behavior of NPs in biological environment, in particular the transport of NPs across biological barriers, including the blood-brain tumor barrier (BBTB), a challenging question. Previous studies have addressed the translocation of NPs of various compositions across cell layers, mostly using only one type of cells. Using a coculture model of the human BBTB, consisting in human cerebral endothelial cells preloaded with ultrasmall superparamagnetic iron oxide nanoparticles (USPIO NPs) and unloaded human glioblastoma cells grown on each side of newly developed ultrathin permeable silicon nitride supports as a model of the human BBTB, we demonstrate for the first time the transfer of USPIO NPs from human brain-derived endothelial cells to glioblastoma cells. The reduced thickness of the permeable mechanical support compares better than commercially available polymeric supports to the thickness of the basement membrane of the cerebral vascular system. These results are the first report supporting the possibility that USPIO NPs could be directly transferred from endothelial cells to glioblastoma cells across a BBTB. Thus, the use of such ultrathin porous supports provides a new in vitro approach to study the delivery of nanotherapeutics to brain cancers. Our results also suggest a novel possibility for nanoparticles to deliver therapeutics to the brain using endothelial to neural cells transfer.

Les traces de pneumatiques en sciences forensiques : de l'analyse chimique à l'évaluation de la force probante

This work is focused on the development of a methodology for the use of chemical characteristic of tire traces to help answer the following question: "Is the offending tire at the origin of the trace found on the crime scene?". This methodology goes from the trace sampling on the road to statistical analysis of its chemical characteristics. Knowledge about the composition and manufacture of tread tires as well as a review of instrumental techniques used for the analysis of polymeric materials were studied to select, as an ansi vi cal technique for this research, pyrolysis coupled to a gas Chromatograph with a mass spectrometry detector (Py-GC/MS). An analytical method was developed and optimized to obtain the lowest variability between replicates of the same sample. Within-variability of the tread was evaluated regarding width and circumference with several samples taken from twelve tires of different brands and/or models. The variability within each of the treads (within-variability) and between the treads (between-variability) could be quantified. Different statistical methods have shown that within-variability is lower than between-variability, which helped differentiate these tires. Ten tire traces were produced with tires of different brands and/or models by braking tests. These traces have been adequately sampled using sheets of gelatine. Particles of each trace were analysed using the same methodology as for the tires at their origin. The general chemical profile of a trace or of a tire has been characterized by eighty-six compounds. Based on a statistical comparison of the chemical profiles obtained, it has been shown that a tire trace is not differentiable from the tire at its origin but is generally differentiable from tires that are not at its origin. Thereafter, a sample containing sixty tires was analysed to assess the discrimination potential of the developed methodology. The statistical results showed that most of the tires of different brands and models are differentiable. However, tires of the same brand and model with identical characteristics, such as country of manufacture, size and DOT number, are not differentiable. A model, based on a likelihood ratio approach, was chosen to evaluate the results of the comparisons between the chemical profiles of the traces and tires. The methodology developed was finally blindly tested using three simulated scenarios. Each scenario involved a trace of an unknown tire as well as two tires possibly at its origin. The correct results for the three scenarios were used to validate the developed methodology. The different steps of this work were useful to collect the required information to test and validate the underlying assumption that it is possible to help determine if an offending tire » or is not at the origin of a trace, by means of a statistical comparison of their chemical profile. This aid was formalized by a measure of the probative value of the evidence, which is represented by the chemical profile of the trace of the tire. - Ce travail s'est proposé de développer une méthodologie pour l'exploitation des caractéristiques chimiques des traces de pneumatiques dans le but d'aider à répondre à la question suivante : «Est-ce que le pneumatique incriminé est ou n'est pas à l'origine de la trace relevée sur les lieux ? ». Cette méthodologie s'est intéressée du prélèvement de la trace de pneumatique sur la chaussée à l'exploitation statistique de ses caractéristiques chimiques. L'acquisition de connaissances sur la composition et la fabrication de la bande de roulement des pneumatiques ainsi que la revue de techniques instrumentales utilisées pour l'analyse de matériaux polymériques ont permis de choisir, comme technique analytique pour la présente recherche, la pyrolyse couplée à un chromatographe en phase gazeuse avec un détecteur de spectrométrie de masse (Py-GC/MS). Une méthode analytique a été développée et optimisée afin d'obtenir la plus faible variabilité entre les réplicas d'un même échantillon. L'évaluation de l'intravariabilité de la bande de roulement a été entreprise dans sa largeur et sa circonférence à l'aide de plusieurs prélèvements effectués sur douze pneumatiques de marques et/ou modèles différents. La variabilité au sein de chacune des bandes de roulement (intravariabilité) ainsi qu'entre les bandes de roulement considérées (intervariabilité) a pu être quantifiée. Les différentes méthodes statistiques appliquées ont montré que l'intravariabilité est plus faible que l'intervariabilité, ce qui a permis de différencier ces pneumatiques. Dix traces de pneumatiques ont été produites à l'aide de pneumatiques de marques et/ou modèles différents en effectuant des tests de freinage. Ces traces ont pu être adéquatement prélevées à l'aide de feuilles de gélatine. Des particules de chaque trace ont été analysées selon la même méthodologie que pour les pneumatiques à leur origine. Le profil chimique général d'une trace de pneumatique ou d'un pneumatique a été caractérisé à l'aide de huitante-six composés. Sur la base de la comparaison statistique des profils chimiques obtenus, il a pu être montré qu'une trace de pneumatique n'est pas différenciable du pneumatique à son origine mais est, généralement, différenciable des pneumatiques qui ne sont pas à son origine. Par la suite, un échantillonnage comprenant soixante pneumatiques a été analysé afin d'évaluer le potentiel de discrimination de la méthodologie développée. Les méthodes statistiques appliquées ont mis en évidence que des pneumatiques de marques et modèles différents sont, majoritairement, différenciables entre eux. La méthodologie développée présente ainsi un bon potentiel de discrimination. Toutefois, des pneumatiques de la même marque et du même modèle qui présentent des caractéristiques PTD (i.e. pays de fabrication, taille et numéro DOT) identiques ne sont pas différenciables. Un modèle d'évaluation, basé sur une approche dite du likelihood ratio, a été adopté pour apporter une signification au résultat des comparaisons entre les profils chimiques des traces et des pneumatiques. La méthodologie mise en place a finalement été testée à l'aveugle à l'aide de la simulation de trois scénarios. Chaque scénario impliquait une trace de pneumatique inconnue et deux pneumatiques suspectés d'être à l'origine de cette trace. Les résultats corrects obtenus pour les trois scénarios ont permis de valider la méthodologie développée. Les différentes étapes de ce travail ont permis d'acquérir les informations nécessaires au test et à la validation de l'hypothèse fondamentale selon laquelle il est possible d'aider à déterminer si un pneumatique incriminé est ou n'est pas à l'origine d'une trace, par le biais d'une comparaison statistique de leur profil chimique. Cette aide a été formalisée par une mesure de la force probante de l'indice, qui est représenté par le profil chimique de la trace de pneumatique.