SE(R)RS devices fabricated by a laser electrodispersion method

A novel laser electrodispersion (LE) technique was employed to deposit gold nanoparticles onto Si and SiOx surfaces. The LE technique combines laser ablation with cascade fission of liquid metal micro-drops, which results in the formation of nanoparticles upon rapid cooling. The shape and the size distribution of the Au nanoparticles prepared by LE depend on the nature of the support. Gold nanoparticles were also deposited in the channels of microreactors fabricated by wet etching of Si and used as SE(R)RS sensors. The influence of the nanoparticle surface density as well as of the nature of the substrate on the Raman response was studied. At an appropriate surface density of the deposited nanoparticles a significant enhancement of Raman signal was observed showing the possibility to create efficient SERS substrates. Application of microfluidic devices in surface enhanced Raman spectroscopy (SERS) in continuous-flow mode with sensor regeneration is described. © 2011 The Royal Society of Chemistry.

Adapting populations of agents

We control a population of interacting software agents. The agents have a strategy, and receive a payoff for executing that strategy. Unsuccessful agents become extinct. We investigate the repercussions of maintaining a diversity of agents. There is often no economic rationale for this. If maintaining diversity is to be successful, i.e. without lowering too much the payoff for the non-endangered strategies, it has to go on forever, because the non-endangered strategies still get a good payoff, so that they continue to thrive, and continue to endanger the endangered strategies. This is not sustainable if the number of endangered ones is of the same order as the number of non-endangered ones. We also discuss niches, islands. Finally, we combine learning as adaptation of individual agents with learning via selection in a population. © Springer-Verlag Berlin Heidelberg 2003.

Stability of multi-agent systems

This work attempts to shed light to the fundamental concepts behind the stability of Multi-Agent Systems. We view the system as a discrete time Markov chain with a potentially unknown transitional probability distribution. The system will be considered to be stable when its state has converged to an equilibrium distribution. Faced with the non-trivial task of establishing the convergence to such a distribution, we propose a hypothesis testing approach according to which we test whether the convergence of a particular system metric has occurred. We describe some artificial multi-agent ecosystems that were developed and we present results based on these systems which confirm that this approach qualitatively agrees with our intuition.

Development of a surface-enhanced raman spectroscopy method for the detection of benzodiazepines in urine

Benzodiazepines are among the most prescribed compounds for anti-anxiety and are present in many toxicological screens. These drugs are also prominent in the commission of drug facilitated sexual assaults due their effects on the central nervous system. Due to their potency, a low dose of these compounds is often administered to victims; therefore, the target detection limit for these compounds in biological samples is 10 ng/mL. Currently these compounds are predominantly analyzed using immunoassay techniques; however more specific screening methods are needed. ^ The goal of this dissertation was to develop a rapid, specific screening technique for benzodiazepines in urine samples utilizing surface-enhanced Raman spectroscopy (SERS), which has previously been shown be capable of to detect trace quantities of pharmaceutical compounds in aqueous solutions. Surface enhanced Raman spectroscopy has the advantage of overcoming the low sensitivity and fluorescence effects seen with conventional Raman spectroscopy. The spectra are obtained by applying an analyte onto a SERS-active metal substrate such as colloidal metal particles. SERS signals can be further increased with the addition of aggregate solutions. These agents cause the nanoparticles to amass and form hot-spots which increase the signal intensity. ^ In this work, the colloidal particles are spherical gold nanoparticles in aqueous solution with an average size of approximately 30 nm. The optimum aggregating agent for the detection of benzodiazepines was determined to be 16.7 mM MgCl2, providing the highest signal intensities at the lowest drug concentrations with limits of detection between 0.5 and 127 ng/mL. A supported liquid extraction technique was utilized as a rapid clean extraction for benzodiazepines from urine at a pH of 5.0, allowing for clean extraction with limits of detection between 6 and 640 ng/mL. It was shown that at this pH other drugs that are prevalent in urine samples can be removed providing the selective detection of the benzodiazepine of interest. ^ This technique has been shown to provide rapid (less than twenty minutes), sensitive, and specific detection of benzodiazepines at low concentrations in urine. It provides the forensic community with a sensitive and specific screening technique for the detection of benzodiazepines in drug facilitated assault cases.^

MACVIA clinical decision algorithm in adolescents and adults with allergic rhinitis

Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.

Development of Plasmonic Nanoplatforms for Diagnostics, Therapy, and Sensing

Recent advances in nanotechnology have led to the application of nanoparticles in a wide variety of fields. In the field of nanomedicine, there is great emphasis on combining diagnostic and therapeutic modalities into a single nanoparticle construct (theranostics). In particular, anisotropic nanoparticles have shown great potential for surface-enhanced Raman scattering (SERS) detection due to their unique optical properties. Gold nanostars are a type of anisotropic nanoparticle with one of the highest SERS enhancement factors in a non-aggregated state. By utilizing the distinct characteristics of gold nanostars, new plasmonic materials for diagnostics, therapy, and sensing can be synthesized. The work described herein is divided into two main themes. The first half presents a novel, theranostic nanoplatform that can be used for both SERS detection and photodynamic therapy (PDT). The second half involves the rational design of silver-coated gold nanostars for increasing SERS signal intensity and improving reproducibility and quantification in SERS measurements.

The theranostic nanoplatforms consist of Raman-labeled gold nanostars coated with a silica shell. Photosensitizer molecules for PDT can be loaded into the silica matrix, while retaining the SERS signal of the gold nanostar core. SERS detection and PDT are performed at different wavelengths, so there is no interference between the diagnostic and therapeutic modalities. Singlet oxygen generation (a measure of PDT effectiveness) was demonstrated from the drug-loaded nanocomposites. In vitro testing with breast cancer cells showed that the nanoplatform could be successfully used for PDT. When further conjugating the nanoplatform with a cell-penetrating peptide (CPP), efficacy of both SERS detection and PDT is enhanced.

The rational design of plasmonic nanoparticles for SERS sensing involved the synthesis of silver-coated gold nanostars. Investigation of the silver coating process revealed that preservation of the gold nanostar tips was necessary to achieve the increased SERS intensity. At the optimal amount of silver coating, the SERS intensity is increased by over an order of magnitude. It was determined that a majority of the increased SERS signal can be attributed to reducing the inner filter effect, as the silver coating process moves the extinction of the particles far away from the laser excitation line. To improve reproducibility and quantitative SERS detection, an internal standard was incorporated into the particles. By embedding a small-molecule dye between the gold and silver surfaces, SERS signal was obtained both from the internal dye and external analyte on the particle surface. By normalizing the external analyte signal to the internal reference signal, reproducibility and quantitative analysis are improved in a variety of experimental conditions.

Development of a Surface-Enhanced Raman Spectroscopy Method for the Detection of Benzodiazepines in Urine

Benzodiazepines are among the most prescribed compounds for anti-anxiety and are present in many toxicological screens. These drugs are also prominent in the commission of drug facilitated sexual assaults due their effects on the central nervous system. Due to their potency, a low dose of these compounds is often administered to victims; therefore, the target detection limit for these compounds in biological samples is 10 ng/mL. Currently these compounds are predominantly analyzed using immunoassay techniques; however more specific screening methods are needed. The goal of this dissertation was to develop a rapid, specific screening technique for benzodiazepines in urine samples utilizing surface-enhanced Raman spectroscopy (SERS), which has previously been shown be capable of to detect trace quantities of pharmaceutical compounds in aqueous solutions. Surface enhanced Raman spectroscopy has the advantage of overcoming the low sensitivity and fluorescence effects seen with conventional Raman spectroscopy. The spectra are obtained by applying an analyte onto a SERS-active metal substrate such as colloidal metal particles. SERS signals can be further increased with the addition of aggregate solutions. These agents cause the nanoparticles to amass and form hot-spots which increase the signal intensity. In this work, the colloidal particles are spherical gold nanoparticles in aqueous solution with an average size of approximately 30 nm. The optimum aggregating agent for the detection of benzodiazepines was determined to be 16.7 mM MgCl2, providing the highest signal intensities at the lowest drug concentrations with limits of detection between 0.5 and 127 ng/mL. A supported liquid extraction technique was utilized as a rapid clean extraction for benzodiazepines from urine at a pH of 5.0, allowing for clean extraction with limits of detection between 6 and 640 ng/mL. It was shown that at this pH other drugs that are prevalent in urine samples can be removed providing the selective detection of the benzodiazepine of interest. This technique has been shown to provide rapid (less than twenty minutes), sensitive, and specific detection of benzodiazepines at low concentrations in urine. It provides the forensic community with a sensitive and specific screening technique for the detection of benzodiazepines in drug facilitated assault cases.

Plus ça change...Le renouvellement de la tradition chez Régine Robin, Dany Laferrière et Ying Chen

Cette thèse analyse la manifestation de la tradition dans certains textes des écrivains migrants au Québec, nommément La Québécoite et L’Immense fatigue des pierres de Régine Robin, Comment faire l’amour avec un nègre sans se fatiguer, Cette grenade dans la main du jeune nègre est-elle une arme ou un fruit ?, Pays sans chapeau et L’Énigme du retour de Dany Laferrière et, enfin L’Ingratitude et Immobile de Ying Chen. Les références à des récits, à des croyances et à des pratiques collectives qui se trouvent dans ces textes signalent une transformation de la transmission de l’héritage culturel d’une génération à l’autre. Afin de parvenir à une meilleure compréhension des liens entre la mémoire collective et la communauté culturelle se définissant dans le présent, je me sers du travail de folkloristes comme Alan Dundes, Simon Bronner et Richard Handler de même que des théories sur la faculté de la tradition proposées par Paul Ricœur, Walter Benjamin et Pierre Nora. Dans la première partie de la thèse, j’étudie l’imaginaire populaire du XIXe siècle et son incorporation dans la littérature canadienne-française de l’époque. Ensuite, j’analyse la remise en question de la tradition – de même que le rôle sous-jacent qu’elle continue de jouer, lors de la Révolution tranquille. Par rapport à ces deux périodes précédentes, l’usage du folklore chez les auteurs migrants laisse présager une nouvelle opération de la tradition dans un contexte où plusieurs groupes culturels se rencontrent. Dans un contexte pluraliste, l’idée de la communauté culturelle est fabriquée en fonction de notre appartenance à plusieurs groupes. Je m’intéresse à comment les gens qui habitent ensemble formulent des liens au passé même dans une situation dans laquelle ils ne partagent pas les mêmes rapports à la mémoire collective. Explorant le renouvellement, qui peut sembler paradoxal, de la tradition, je forme l’hypothèse qu’il est possible pour un groupe de se définir en fonction de valeurs culturelles puisées dans un passé collectif qui s’adaptent constamment à la réalité actuelle.

Polifemo en Yucatán. Variaciones sobre un episodio de la Eneida en la épica cortesiana del Quinientos

Entre los modelos literarios que, en las epopeyas quinientistas acerca de la conquista de México, sirven para dar forma épica a la materia histórica tomada de las crónicas, la Eneida de Virgilio desempeña un papel fundamental. En el presente artículo se pretende mostrar cómo la identificación de Jerónimo de Aguilar con el Aqueménides virgiliano, que se encuentra por primera vez en el Carlo famoso de Luis Zapata, reaparece en Francisco de Terrazas, en Gabriel Lobo Lasso de la Vega y en Antonio de Saavedra Guzmán, así como proponer algunas consideraciones acerca de las relaciones que se hayan podido dar entre las obras de estos poetas.

Surface-Enhanced Raman Spectroscopy as a Probe of the Surface Chemistry of Nanostructured Materials

Surface-enhanced Raman spectroscopy (SERS) is now widely used as a rapid and inexpensive tool for chemical/biochemical analysis. The method can give enormous increases in the intensities of the Raman signals of low-concentration molecular targets if they are adsorbed on suitable enhancing substrates, which are typically composed of nanostructured Ag or Au. However, the features of SERS that allow it to be used as a chemical sensor also mean that it can be used as a powerful probe of the surface chemistry of any nanostructured material that can provide SERS enhancement. This is important because it is the surface chemistry that controls how these materials interact with their local environment and, in real applications, this interaction can be more important than more commonly measured properties such as morphology or plasmonic absorption. Here, the opportunity that this approach to SERS provides is illustrated with examples where the surface chemistry is both characterized and controlled in order to create functional nanomaterials.

Raman Analysis of Dilute Aqueous Samples by Localized Evaporation of Submicroliter Droplets on the Tips of Superhydrophobic Copper Wires

Raman analysis of dilute aqueous solutions is normally prevented by their low signal levels. A very general method to increase the concentration to detectable levels is to evaporate droplets of the sample to dryness, creating solid deposits which are then Raman probed. Here, superhydrophobic (SHP) wires with hydrophilic tips have been used as supports for drying droplets, which have the advantage that the residue is automatically deposited at the tip. The SHP wires were readily prepared in minutes using electroless galvanic deposition of Ag onto copper wires followed by modification with a polyfluorothiol (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-decanethiol, HDFT). Cutting the coated wires with a scalpel revealed hydrophilic tips which could support droplets whose maximum size was determined by the wire diameter. Typically, 230 μm wires were used to support 0.6 μL droplets. Evaporation of dilute melamine droplets gave solid deposits which could be observed by scanning electron microscopy (SEM) and Raman spectroscopy. The limit of detection for melamine using a two stage evaporation procedure was 1 × 10^-6 mol dm^-3. The physical appearance of dried droplets of sucrose and glucose showed that the samples retained significant amounts of water, even under high vacuum. Nonetheless, the Raman detection limits of sucrose and glucose were 5 × 10^-4 and 2.5 × 10^-3 mol dm^-3, respectively, which is similar to the sensitivity reported for surface-enhanced Raman spectroscopy (SERS) detection of glucose. It was also possible to quantify the two sugars in mixtures at concentrations which were similar to those found in human blood through multivariate analysis.

Swellable polymer films containing Au nanoparticles for point-of-care therapeutic drug monitoring using surface-enhanced Raman spectroscopy

Large (10 × 10 cm) sheets of surface-enhanced Raman spectroscopy (SERS) active polymer have been prepared by stabilising metal nanoparticle aggregates within dry hydroxyethylcellulose (HEC) films. In these films the aggregates are protected by the polymer matrix during storage but in use they are released when aqueous analyte droplets cause the films to swell to their gel form. The fact that these "Poly-SERS" films can be prepared in bulk but then cut to size and stored in air before use means that they provide a cost effective and convenient method for routine SERS analysis. Here we have tested both Ag and Au Poly-SERS films for use in point-of-care monitoring of therapeutic drugs, using phenytoin as the test compound. Phenytoin in water could readily be detected using Ag Poly-SERS films but dissolving the compound in phosphate buffered saline (PBS) to mimic body fluid samples caused loss of the drug signal due to competition for metal surface sites from Cl^- ions in the buffer solution. However, with Au Poly-SERS films there was no detectable interference from Cl^- and these materials allowed phenytoin to be detected at 1.8 mg L^-1, even in PBS. The target range of detection of phenytoin in therapeutic drug monitoring is 10-20 mg L^-1. With the Au Poly-SERS films, the absolute signal generated by a given concentration of phenytoin was lower for the films than for the parent colloid but the SERS signals were still high enough to be used for therapeutic monitoring, so the cost in sensitivity for moving from simple aqueous colloids to films is not so large that it outweighs the advantages which the films bring for practical applications, in particular their ease of use and long shelf life.

Surface-enhanced Raman spectroscopy of novel psychoactive substances using polymer-stabilized Ag nanoparticle aggregates

A set of seized "legal high'' samples and pure novel psychoactive substances have been examined by surface-enhanced Raman spectroscopy using polymer-stabilized Ag nanoparticle (Poly-SERS) films. The films both quenched fluorescence in bulk samples and allowed identification of mu g quantities of drugs collected with wet swabs from contaminated surfaces.

A oratória da mulher indígena: um estudo da narrativa autobiográfica Bobbi Lee: Indian Rebel, de Lee Maracle

Atualmente, o indivíduo está rodeado por inúmeros discursos sociais, e o trabalho literário é a maneira pela qual o escritor demonstra um ponto de vista. Essa característica define a literatura como uma ferramenta ideológica, negando sua existência como produção imparcial, característica que adiciona a qualquer produto literário um significado social. A ideologia do autor não é expressa somente através da narração, ela também é percebida pelo manejo com que ele/ela lida com os componentes estruturais do texto. Como qualquer prática social, o gênero literário é passível de mudanças em sua estrutura, acarretando novos significados. Levando em conta esse aspecto do discurso literário, esta dissertação irá observar no texto autobiográfico Bobbi Lee: Indian Rebel, de Lee Maracle, como a presença de traços oriundos da contação de estória altera a estrutura do texto autobiográfico, conforme definido por Philippe Lejeune, incorporando características do Künstlerroman. Junto a isso, serão observadas as ações da protagonista em busca de uma nova perspectiva que lhe possibilite definir-se como mulher indígena, em oposição ao comportamento de sua mãe e sua irmã Joyce. Através de sua trajetória pessoal, a protagonista mostra os esforços dos ameríndios para terem reconhecido seu lugar como sujeito político no Canadá.

Training-related risk of common illnesses in elite swimmers over a 4-yr period