Exploring oligo(p-phenylenevinylene) gelators as sensors and stimuli responsive materials

Gelation provides a unique medium, which often induces organization of molecules resulting in the modulation of their optical, morphological and electronic properties thereby opening a new world of fascinating materials with interesting physical properties at nano- meso- and macroscopic levels. Supramolecular gels based on linear π-systems have attracted much attention due to their inherent optical and electronic properties which find application in organic electronics, light harvesting and sensing. They exhibit reversible properties due to the dynamic nature of noncovalent forces. As a result, studies on such soft materials are currently a topic of great interest. Recently, researchers are actively involved in the development of sensors and stimuli-responsive materials based on self-assembled π-systems, which are also called smart materials. The present thesis is divided into four chapters

Self-Assembly of Stimuli-Responsive Water-Soluble [60]Fullerene End-Capped Ampholytic Block Copolymer

Well-defined, water-soluble, pH and temperature stimuli-responsive [60]fullerene (C₆₀) containing ampholytic block copolymer of poly((methacrylic acid)-block-(2-(dimethylamino)ethyl methacrylate))-block–C₆₀ (P(MAA-b-DMAEMA)-b-C₆₀) was synthesized by the atom transfer radical polymerization (ATRP) technique. The self-assembly behaviour of the C₆₀ containing polyampholyte in aqueous solution was characterized by dynamic light scattering (DLS), and transmission electron microscopy. This amphiphilic mono-C₆₀ end-capped block copolymer shows enhanced solubility in aqueous medium at room and elevated temperatures and at low and high pH but phase-separates at intermediate pH of between 5.4 and 8.8. The self assembly of the copolymer is different from that of P(MAA-b-DMAEMA). Examination of the association behavior using DLS revealed the co-existence of unimers and aggregates at low pH at all temperatures studied, with the association being driven by the balance of hydrophobic and electrostatic interactions. Unimers and aggregates of different microstructures are also observed at high pH and at temperatures below the lower critical solution temperature (LCST) of PDMAEMA. At high pH and at temperatures above the LCST of PDMAEMA, the formation of micelles and aggregates co-existing in solution is driven by the combination of hydrophobic, electrostatic, and charge-transfer interactions.

Stimuli-responsive Novel Amphiphilic Polymers for Chemical and Biomedical Applications

Amphiphilic polymers are a class of polymers that self-assemble into different types of microstructure, depending on the solvent environment and external stimuli. Self assembly structures can exist in many different forms, such as spherical micelles, rod-like micelles, bi-layers, vesicles, bi-continuous structure etc. Most biological systems are basically comprised of many of these organised structures arranged in an intelligent manner, which impart functions and life to the system. We have adopted the atom transfer radical polymerization (ATRP) technique to synthesize various types of block copolymer systems that self-assemble into different microstructure when subject to an external stimuli, such as pH or temperature. The systems that we have studied are: (1) pH responsive fullerene (C60) containing poly(methacrylic acid) (PMAA-b-C60); (2) pH and temperature responsive fullerene containing poly[2-(dimethylamino)ethyl methacrylate] (C₆₀-b-PDMAEMA); (3) other responsive water-soluble fullerene systems. By varying temperature, pH and salt concentration, different types microstructure can be produced. In the presence of inorganic salts, fractal patterns at nano- to microscopic dimension were observed for negatively charged PMAA-b-C60, while such structure was not observed for positively charged PDMAEMA-b-C60. We demonstrated that negatively charged fullerene containing polymeric systems can serve as excellent nano-templates for the controlled growth of inorganic crystals at the nano- to micrometer length scale and the possible mechanism was proposed. The physical properties and the characteristics of their self-assembly properties will be discussed, and their implications to chemical and biomedical applications will be highlighted.

Targeted Stimuli-Responsive Dextran Conjugates for Doxorubicin Delivery to Hepatocytes

A targeted, stimuli-responsive, polymeric drug delivery vehicle is being developed in our lab to help alleviate severe side-effects caused by narrow therapeutic window drugs. Targeting specific cell types or organs via proteins, specifically, lectin-mediated targeting holds potential due to the high specificity and affinity of receptor-ligand interactions, rapid internalization, and relative ease of processing. Dextran, a commercially available, biodegradable polymer has been conjugated to doxorubicin and galactosamine to target hepatocytes in a three-step, one-pot synthesis. The loading of doxorubicin and galactose on the conjugates was determined by absorbance at 485 nm and elemental analysis, respectively. Conjugation efficiency based on the amount loaded of each reactant varies from 20% to 50% for doxorubicin and from 2% to 20% for galactosamine. Doxorubicin has also been attached to dextran through an acid-labile hydrazide bond. Doxorubicin acts by intercalating with DNA in the nuclei of cells. The fluorescence of doxorubicin is quenched when it binds to DNA. This allows a fluorescence-based cell-free assay to evaluate the efficacy of the polymer conjugates where we measure the fluorescence of doxorubicin and the conjugates in increasing concentrations of calf thymus DNA. Fluorescence quenching indicates that our conjugates can bind to DNA. The degree of binding increases with polymer molecular weight and substitution of doxorubicin. In cell culture experiments with hepatocytes, the relative uptake of polymer conjugates was evaluated using flow cytometry, and the killing efficiency was determined using the MTT cell proliferation assay. We have found that conjugate uptake is much lower than that of free doxorubicin. Lower uptake of conjugates may increase the maximum dose of drug tolerated by the body. Also, non-galactosylated conjugate uptake is lower than that of the galactosylated conjugate. Microscopy indicates that doxorubicin localizes almost exclusively at the nucleus, whereas the conjugates are present throughout the cell. Doxorubicin linked to dextran through a hydrazide bond was used to achieve improved killing efficiency. Following uptake, the doxorubicin dissociates from the polymer in an endosomal compartment and diffuses to the nucleus. The LC₅₀ of covalently linked doxorubicin is 7.4 μg/mL, whereas that of hydrazide linked doxorubicin is 4.4 μg/mL.

Aplicació del càlcul d’esforços en 2n ordre en estructures metàl·liques segons el CTE i NBE-EA-95

Aquest estudi se centra en el document del CTE que es refereix a les estructures metàl·liques d’acer, concretament en els càlculs a tenir en compte a l’hora de realitzar pòrtics d’estructura d’edificació amb perfils metàl·lics laminats. Aquest document és el DB-SE-A, que són les sigles de “Document Bàsic Seguretat Estructural Acer”. Aquest document introdueix algunes modificacions en el mètode de càlcul de les estructures metàl·liques respecte l’antiga norma. La idea d’aquest estudi és fer una comparació entre les dues normes – la vella i ja derogada, i la nova i vigent – i com tracten el càlcul d’esforços en segon ordre i el tractament de les imperfeccions. Com ja s’ha comentat aquest Document Bàsic de la Seguretat Estructural en Acer del CTE (DB-SE-A) substitueix l’antiga norma que es referia al càlcul d’estructura metàl·lica, la NBE-EA-95. En l’aplicació de les accions i el càlcul d’esforços s’utilitza del CTE el Document Bàsic dedicat a les accions en l’edificació (DB-SE-AE) i que substitueix l’antiga NBE-AE-88

Derived control by compound and single stimuli in a matching-to-sample task in children

Resumen tomado de la publicaci??n

L'Ordre dels constituents sintàctics oracionals majors en català

El treball és la primera part d’una tesi que tractarà la influència que la llengua materna (L1) pot exercir en l’adquisició de la segona llengua (L2). Concretament, la tesi se centrarà en la influència de les característiques gramaticals del panjabi i del romanès com a L1 en l’adquisició de l’ordre sintàctic del català com a L2. El treball de recerca descriu alguns aspectes de l’ordre sintàctic del català a partir de gramàtiques, de treballs específics sobre el tema, de l’anàlisi d’un corpus oral i del meu propi coneixement de la llengua com a parlant. Concretament s’estudien les oracions principals i les subordinades completives dependents de verbs com dir, suposar o pensar

Global and dominance with concentric hierarchical stimuli and orientation classification task. 'Dominancia global y local con est??mulos conc??ntricos y tareas de clasificaci??n de la orientaci??n'

Resumen tomado de la publicaci??n. Resumen tambi??n en ingl??s

Emotional stimuli reduce the attentional blink in sub-clinical anxious subjects. 'Los est??mulos emocionales reducen el parpadeo atencional (attentional blink) en sujetos con ansiedad subcl??nica'

Resumen tomado de la publicaci??n

L'entorn sonor, un element educatiu de primer ordre. 'El entorno sonoro, un elemento educativo de primer orden'.

Resumen de la revista

Entorn i imatge artística. Pintar : recobrir una superfície de colors amb un cert ordre. L'artista dona una nova visió de les formes. 'Entorno e imagen artística. Pintar : recubrir una superficie de colores con un cierto orden. El artista da una nueva visión de las formas'.

Crédito del área de Educación Visual y Plástica. Divide el crédito en 2 niveles de concreción y desarrolla extensamente el segundo. El objetivo es acercarse a la Pintura y entenderla dentro de la Educación Artística. Se establece entre los temas una coherencia-guión teoría y prácticas y una secuencia de actividades de aprendizaje. Las actividades de evaluación coinciden con algunas actividades prácticas.

L’ ordre de clítics en català antic: morfologia i sintaxi dels clítics pronominals en català medieval

L'ordre dels cíclics en la llengua catalana medieval

Ordre de mots i estructura informativa a la llengua de Francesc Eiximenis

En aquest estudi s’examina la llengua d’alguns textos de Francesc Eiximenis (concretament, el ‘Dotzè del Crestià’ i les cartes autògrafes publicades per Martí 2002) per tal d’aprofundir en la distribució de l’estructura informativa i el consegüent ordre de mots que utilitza l’autor. L’objectiu d’aquesta comunicació és aprofundir en els casos d’ avantposició del català antic que correspon a una estructura de focalització feble (no contrastiva)

Attentional orienting to biologically fear-relevant stimuli: data from eye tracking

Snakes are thought as fear-relevant stimuli (biologically prepared to be associated with fear) which can lead to an enhanced attentional capture when compared fear-irrelevant stimuli. Inherent limitations related to the key-press behaviour might be bypassed with the measurement of eye movements, since they are more closely related to attentional processes than reaction times. An eye tracking technique was combined with the flicker paradigm in two studies. A sample of university students was gathered. In both studies, an instruction to detect changes between the pair of scenes was given. Attentional orienting for the changing element in the scene was analyzed, as well the role of fear of snakes as a moderator variable. The results for both studies revealed a significant shorter time to first fixation for snake stimuli when compared to control stimuli. A facilitating effect of fear of snakes was also found for snakes, presenting the highly fear participants a shorter a time to first fixation for snake stimuli when compared to low-feared participants. The results are in line with current research that supports the advantage of snakes to grab attention due their evo-biological significance.