Bovine primary chondrocyte culture in synthetic matrix metalloproteinase-sensitive poly(ethylene glycol)-based hydrogels as a scaffold for cartilage repair

A poly(ethylene glycol) (PEG)-based hydrogel was used as a scaffold for chondrocyte culture. Branched PEG-vinylsulfone macromers were end-linked with thiol-bearing matrix metalloproteinase (MMP)-sensitive peptides (GCRDGPQGIWGQDRCG) to form a three-dimensional network in situ under physiologic conditions. Both four- and eight-armed PEG macromer building blocks were examined. Increasing the number of PEG arms increased the elastic modulus of the hydrogels from 4.5 to 13.5 kPa. PEG-dithiol was used to prepare hydrogels that were not sensitive to degradation by cell-derived MMPs. Primary bovine calf chondrocytes were cultured in both MMP-sensitive and MMP-insensitive hydrogels, formed from either four- or eight-armed PEG. Most (>90%) of the cells inside the gels were viable after 1 month of culture and formed cell clusters. Gel matrices with lower elastic modulus and sensitivity to MMP-based matrix remodeling demonstrated larger clusters and more diffuse, less cell surface-constrained cell-derived matrix in the chondron, as determined by light and electron microscopy. Gene expression experiments by real-time RT-PCR showed that the expression of type II collagen and aggrecan was increased in the MMP-sensitive hydrogels, whereas the expression level of MMP-13 was increased in the MMP-insensitive hydrogels. These results indicate that cellular activity can be modulated by the composition of the hydrogel. This study represents one of the first examples of chondrocyte culture in a bioactive synthetic material that can be remodeled by cellular protease activity.

Multiscale methods for shape constraints in deconvolution: Confidence statements for qualitative features

We derive multiscale statistics for deconvolution in order to detect qualitative features of the unknown density. An important example covered within this framework is to test for local monotonicity on all scales simultaneously. We investigate the moderately ill-posed setting, where the Fourier transform of the error density in the deconvolution model is of polynomial decay. For multiscale testing, we consider a calibration, motivated by the modulus of continuity of Brownian motion. We investigate the performance of our results from both the theoretical and simulation based point of view. A major consequence of our work is that the detection of qualitative features of a density in a deconvolution problem is a doable task, although the minimax rates for pointwise estimation are very slow.

Minor ampullate silks from Nephila and Argiope spiders: tensile properties and microstructural characterization

The mechanical behavior and microstructure of minor ampullate gland silk (miS) of two orb-web spinning species, Argiope trifasciata and Nephila inaurata, were extensively characterized, enabling detailed comparison with other silks. The similarities and differences exhibited by miS when compared with the intensively studied major ampullate gland silk (MAS) and silkworm (Bombyx mori) silk offer a genuine opportunity for testing some of the hypotheses proposed to correlate microstructure and tensile properties in silk. In this work, we show that miSs of different species show similar properties, even when fibers spun by spiders that diverged over 100 million years are compared. The tensile properties of miS are comparable to those of MAS when tested in air, significantly in terms of work to fracture, but differ considerably when tested in water. In particular, miS does not show a supercontraction effect and an associated ground state. In this regard, the behavior of miS in water is similar to that of B. mori silk, and it is shown that the initial elastic modulus of both fibers can be explained using a common model. Intriguingly, the microstructural parameters measured in miS are comparable to those of MAS and considerably different from those found in B. mori. This fact suggests that some critical microstructural information is still missing in our description of silks, and our results suggest that the hydrophilicity of the lateral groups or the large scale organization of the sequences might be routes worth exploring.

An anodeless (bare) tether experiment

NETT (New Electrodynamic Tether Technology) is an experiment proposed to ESA in 1991 as part of the Columbus Precursor Flights. It was originally intended to fly as an exposed payload in the Shuttle cargo bay. The main purpose was to demonstrate the electrodynamical capabilities of the innovative "bare tether" concept. The proposed conceptual design was recommended by a Scientific Panel of ESA, meeting in Heidelberg in March 1992. Unfortunately, the Precursor Flights have all but been scuttled, particularly as far as exposed payloads are concerned. The experiment, horever, is being considered in accomodation studies (APLSS, PIERS) for the European modulus of the future Space Station. Additionally, it might be possible to fly the bare tether in a Russian spacecraft.

Modelo gráfico para la datación de vías romanas empedradas a partir del estudio de sus estados de frecuentación y del análisis superficial de roderas

La presente tesis doctoral se orienta al estudio y análisis de los caminos empedrados antiguos, desde la época prerromana, tanto desde el punto de vista histórico como desde el técnico. La cuantificación de la romanidad de un camino representa un objetivo importante para la mayoría de los estudiosos de la caminería antigua, así como para los arqueólogos, por los datos que ofrece acerca del uso del territorio, los trazados de caminos en la antigüedad y los tráficos asociados. Cuantificar la romanidad de un camino no es tarea sencilla debido a que intervienen multitud de condicionantes que están vivos y son cambiantes como consecuencia del dinamismo inherente al propio camino. En cuanto al aspecto histórico, se realiza una descripción y análisis de la evolución del camino en la Península Ibérica desde sus orígenes hasta mediados del siglo XX, que permite diferenciar la red itineraria según su momento histórico. Así mismo, se describen y analizan: las ruedas y los carros desde sus orígenes, especialmente en la época romana -incluyendo una toma de medidas de distintos tipos de carro, existentes en instituciones y colecciones particulares-; las técnicas de transporte en la antigüedad y las características de la infraestructura viaria de época romana, detallando aspectos generales de sus técnicas de ingeniería y construcción. Desde el punto de vista técnico, el enfoque metodológico ha sido definir un Índice de Romanidad del Camino (IRC) para la datación de vías romanas empedradas, basado en un análisis multicriterio, a partir de los distintos factores que caracterizan su romanidad. Se ha realizado un exhaustivo estudio de campo, con la correspondiente toma de datos en las vías. Se han realizado una serie de ensayos de laboratorio con un prototipo creado exprofeso para simular el desgaste de la piedra producido por el traqueteo del carro al circular por el camino empedrado y dar una hipótesis de datación del camino. Se ha realizado un tratamiento estadístico con la muestra de datos medidos en campo. Se ha definido además el concepto de elasticidad de rodera usando la noción de derivada elástica. En cuanto a los resultados obtenidos: se ha calculado el Índice de Romanidad del Camino (IRC) en una serie de vías empedradas, para cuantificar su romanidad, obteniéndose un resultado coherente con la hipótesis previa sobre la datación de dichas vías; y se ha formulado un modelo exponencial para el número de frecuentaciones de carga que lo relaciona con la elasticidad de rodera y con su esbeltez y que se ha utilizado para relacionar la elasticidad de la rodera con la geología de la roca. Se ha iniciado una línea de investigación sobre la estimación de tráficos históricos en la caminería antigua, considerando que el volumen de tráfico a lo largo del tiempo en un tramo de vía está relacionado con los valores de elasticidad de rodera de dicho tramo a través de la tipología de la roca. En resumen, la presente tesis doctoral proporciona un método para sistematizar el estudio de los caminos antiguos, así como para datarlos y estimar la evolución de sus tráficos. The present Ph. D. Thesis aims to study and to analyze ancient cobbled ways, since pre-roman times, both from the historical and technical points of view. The quantification of the Roman character of a way represents an important target for most of the researchers of ancient ways, as well as for the archaeologists, due to information that it offers about the use of the territory, the tracings of ways in the antiquity and the associate flows. To quantify the Roman character of a way is not a simple task because it involves multitude of influent factors that are alive and variable as a result of the dynamism inherent to the way. As for the historical aspect, a description and analysis of the evolution of the way in the Iberian Peninsula from its origins until the middle of the twentieth century has been done. This allows us to distinguish between elements of the network according to its historical moment. Likewise, a description and analysis is given about: the wheels and the cars since their origins, especially in the Roman time - including a capture of measurements of different types of car, belonging to institutions and to particular collections-; the transport techniques on the antiquity and the characteristics of the road infrastructure of Roman epoch, detailing general technical engineering and constructive aspects. From the technical point of view, the methodological approach has been to define an Index of the Roman Character of the Way (IRC) for the dating of cobbled Roman routes, based on a multi-criterion analysis, involving different factors typical of Roman ways. An exhaustive field study has been realized, with the corresponding capture of information in the routes. A series of laboratory essays has been realized with an ad hoc prototype created to simulate the wear of the stone produced by cars circulating along the cobbled way, and to give a dating hypothesis of the way. A statistical treatment has been realized with the sample of information measured in field. There has been defined also the concept of elasticity of rolling trace using the notion of elastic derivative. As for the obtained results: there has been calculated the Index of Roman Character of the Way (IRC) in a series of cobbled routes, to quantify its Roman character, obtaining a coherent result with the previous dating hypothesis of the above mentioned routes; and an exponential model has been formulated for the number of frequent attendances of load that relates this number to the elasticity of rolling trace and to its slenderness and that has been used to relate the elasticity of the rolling trace to the geology of the rock. An investigation line has been opened about the estimation of historical flows in ancient ways, considering that the traffic volume over the course of time in a route stretch is related to the values of elasticity of rolling trace of the above mentioned stretch by means of the typology of the rock. In short, the present Ph. D. Thesis provides a method to systematize the study of ancient ways, as well as to date them and to estimate the evolution of their flows.

An inverse optimization strategy to determine single crystal mechanical behavior from polycrystal tests: Application to AZ31 Mg alloy

An inverse optimization strategy was developed to determine the single crystal properties from experimental results of the mechanical behavior of polycrystals. The polycrystal behavior was obtained by means of the finite element simulation of a representative volume element of the microstructure in which the dominant slip and twinning systems were included in the constitutive equation of each grain. The inverse problem was solved by means of the Levenberg-Marquardt method, which provided an excellent fit to the experimental results. The iterative optimization process followed a hierarchical scheme in which simple representative volume elements were initially used, followed by more realistic ones to reach the final optimum solution, leading to important reductions in computer time. The new strategy was applied to identify the initial and saturation critical resolved shear stresses and the hardening modulus of the active slip systems and extension twinning in a textured AZ31 Mg alloy. The results were in general agreement with the data in the literature but also showed some differences. They were partially explained because of the higher accuracy of the new optimization strategy but it was also shown that the number of independent experimental stress-strain curves used as input is critical to reach an accurate solution to the inverse optimization problem. It was concluded that at least three independent stress-strain curves are necessary to determine the single crystal behavior from polycrystal tests in the case of highly textured Mg alloys.

Refuerzo de vigas de hormigón armado mediante la aplicación de fuerzas exteriores introducidas por predeformación de perfiles metálicos

Una técnica de refuerzo de elementos flectados en general y, en particular, de vigas y forjados de hormigón armado, consiste en la disposición de perfiles metálicos por debajo de los elementos a reforzar y retacados a ellos. En muchos casos este refuerzo se diseña con un planteamiento pasivo, es decir, los perfiles no entran en carga hasta que no se incrementan las acciones sobre el elemento reforzado, o lo hacen sólo ligeramente y de forma cuantitativamente no controlada efectuando el retacado mediante cuñas metálicas. En el presente trabajo se estudia la alternativa del refuerzo de vigas de hormigón armado frente a momentos flectores con un planteamiento activo, introduciendo unas fuerzas (por ejemplo, mediante gatos o barras roscadas) entre el perfil y el elemento a reforzar, y retacando posteriormente el perfil a la viga en los puntos de introducción de las fuerzas, mediante cuñas metálicas, mortero, etc. La propuesta que formulamos en el presente trabajo de investigación para el control de las fuerzas introducidas consiste en la medida de las flechas que se producen en el perfil metálico al hacerlo reaccionar contra la viga. Esto permite el empleo de procedimientos sencillos para la predeformación del perfil que no dispongan de dispositivos de medida de la carga introducida, o bien controlar la veracidad de las medidas de las fuerzas que dan tales dispositivos. La gran fiabilidad que tiene el cálculo de flechas en jácenas metálicas hace que con este procedimiento se puedan conocer con gran precisión las fuerzas introducidas. Las medidas de las flechas se pueden llevar a cabo mediante los procedimientos de instrumentación habituales en pruebas de carga, con una precisión más que suficiente para conocer y controlar con fiabilidad el valor de las fuerzas que el perfil ejerce sobre la viga. Los perfiles necesarios para el refuerzo con esta técnica son netamente inferiores a los que se precisarían con el planteamiento pasivo antes indicado. En el trabajo de investigación se recoge un estudio sobre el número, posición y valor de las fuerzas de refuerzo a introducir, en función de la carga para la que se diseña el refuerzo y la capacidad resistente del elemento a reforzar, y se analizan los valores máximos que pueden tener dichas fuerzas, en función de la capacidad de la pieza frente a momentos de signo contrario a los debidos a las cargas gravitatorias. A continuación se analiza la interacción viga-perfil al incrementarse las cargas sobre la viga desde el instante de la ejecución del refuerzo, interacción que hace variar el valor de las fuerzas que el perfil ejerce sobre la viga. Esta variación permite contar con un incremento en las fuerzas de refuerzo si, con las cargas permanentes presentes al reforzar, no podemos introducirlas inicialmente con el valor necesario, o si se producen pérdidas en las propias fuerzas. Este es uno de los criterios a la hora de seleccionar las características del perfil. Por el contrario, dicha variación puede suponer que en algunos puntos a lo largo del vano se supere la capacidad a flexión frente a momentos de signo contrario a los debidos a las cargas gravitatorias, lo que también debe ser tenido en cuenta. Seguidamente se analizan diferentes aspectos que producen una variación en el valor de las fuerzas de refuerzo, como son las deformaciones diferidas del hormigón (fluencia y retracción), los gradientes de temperatura en la pieza, o la actuación de sobrecargas en los vanos adyacentes. Se concluye los efectos de estos fenómenos, que en ocasiones tienen gran influencia, pueden ser cuantificados por el proyectista, recogiéndose propuestas sencillas para su consideración en casos habituales. Posteriormente recogemos una propuesta de metodología de comprobación del refuerzo, en cuanto a cómo considerar la fisuración y evolución del módulo de deformación de la viga, la introducción de la seguridad, la influencia de las tolerancias de laminación en el perfil sobre el valor calculado de las flechas necesarias en el perfil para introducir las fuerzas iniciales proyectadas, o la situación accidental de fuego, entre otros aspectos. Por último, se exponen las conclusiones más relevantes de la investigación realizada, y se proponen futuras líneas de investigación. One technique for strengthening flexural members in general, and reinforced concrete beams and slabs in particular, entails caulking the underside of these members with steel shapes. This sort of strengthening is often designed from a passive approach; i.e., until the load is increased, the shapes are either not loaded or are only slightly loaded to some unquantified extent by caulking with steel shims. The present study explored the possibility of actively strengthening the capacity of reinforced concrete beams to resist bending moments by applying forces (with jacks or threaded bars, for instance) between the shape and the member to be strengthened. The shape is subsequently caulked under the beam at the points where the forces are applied with steel shims, mortar or similar. The proposal put forward in the present study to monitor the forces applied consists in measuring the deflection on the steel shape as it reacts against the beam. With this technique, the shape can be pre-strained using simple procedures that do not call for devices to measure the force applied, or the accurancy of the respective measurements can be verified. As deflection calculations in steel girders are extremely reliable, the forces applied with this procedure can be very precisely determined. Standard instrumental procedures for load testing can be used to measure deflection with more than sufficient precision to reliably determine and monitor the value of the forces exerted on the beam by the shape. Moreover, the shapes required to strengthen members with this technique are substantially smaller than the ones needed in the aforementioned passive approach. This study addressed the number, position and value of the strengthening forces to be applied in terms of the load for which strengthening was designed and the bearing capacity of the member to be strengthened. The maximum value of such forces was also analysed as a function of the capacity of the member to resist counter-gravity moments. An analysis was then conducted of beam-shape interaction when the load on the beam raises since the instant that strengthening is applied, interaction that alters the forces applied to the beam by the shape. This variation can provide an increment in the forces if we cannot introduce them initially with the value calculated as necessary because they were limited by the permanent loads existing when strengthening, or if losses occur in the forces themselves. This is one of the criteria for defining shape specifications. Conversely, such variation may cause the forces to exceed beam counter-gravity bending strength at some points in the span, a development that must also be taken into consideration. Other factors inducing variations in the strengthening force values were then analysed, including deferred concrete strain (creep and shrinkage), temperature gradients in the member and the live loads acting on adjacent spans. The inference drawn was that these developments, which may on occasion have a heavy impact, can be quantified by the design engineer, particularly in ordinary situations, for which simple procedures are proposed. Methodology is likewise proposed for verifying strength in terms of how to appraise beam's cracking and variations in modulus of deformation; safety concerns; the effect of shape lamination tolerance on the calculated deflection necessary for the shape to apply the design forces; and fire-induced situations, among others. Lastly, the most prominent conclusions are discussed and future lines of research are suggested.

Pulling a single chromatin fiber reveals the forces that maintain its higher-order structure

Single chicken erythrocyte chromatin fibers were stretched and released at room temperature with force-measuring laser tweezers. In low ionic strength, the stretch-release curves reveal a process of continuous deformation with little or no internucleosomal attraction. A persistence length of 30 nm and a stretch modulus of ≈5 pN is determined for the fibers. At forces of 20 pN and higher, the fibers are modified irreversibly, probably through the mechanical removal of the histone cores from native chromatin. In 40–150 mM NaCl, a distinctive condensation-decondensation transition appears between 5 and 6 pN, corresponding to an internucleosomal attraction energy of ≈2.0 kcal/mol per nucleosome. Thus, in physiological ionic strength the fibers possess a dynamic structure in which the fiber locally interconverting between “open” and “closed” states because of thermal fluctuations.

Globular cluster ages

We review two new methods to determine the age of globular clusters (GCs). These two methods are more accurate than the classical isochrone fitting technique. The first method is based on the morphology of the horizontal branch and is independent of the distance modulus of the globular cluster. The second method uses a careful binning of the stellar luminosity function and determines simultaneously the distance and age of the GC. We find that the oldest galactic GCs have an age of 13.5 ± 2 gigayears (Gyr). The absolute minimum age for the oldest GCs is 10.5 Gyr (with 99% confidence) and the maximum 16.0 Gyr (with 99% confidence). Therefore, an Einstein–De Sitter Universe (Ω = 1) is not totally ruled out if the Hubble constant is about 65 ± 10 Km s−1 Mpc−1.

Estudo da blenda PBAT/PLA com cargas.

Neste trabalho compósitos foram obtidos a partir da blenda comercial 100% biodegradável Ecovio® C2224 da BASF, uma blenda formada por 55% em massa de um copoliéster biodegradável, o Ecoflex® (poli[(adipato de butileno)-co-(tereftalato de butileno)]) e 45% em massa de PLA poli(ácido láctico). Como carga, utilizaram-se dois tipos de argilas comerciais do grupo das esmectitas, ambas predominantemente montmorilonitas: Cloisite Sódica® e Cloisite 30B®. Também foi utilizado como carga a sílica coloidal comercial Aerosil 200®, com área superficial de 200 m2/g e diâmetro médio de partícula 12nm. Os compósitos estudados, ambos contendo 5% e 10% em massa de cargas, foram preparados em uma extrusora de rosca dupla, acoplada a um reômetro de torque. O estudo foi dividido em três etapas: 1ª) etapa: Obtenção e caracterização dos compósitos de Ecovio®/ argila e Ecovio® / sílica; 2ª) etapa: Avaliação da fotodegradação do Ecovio® puro e dos compósitos obtidos; 3ª) etapa: Avaliação da biodegradabilidade do Ecovio® puro e dos compósitos após exposição em câmara de UV. As propriedades mecânicas dos compósitos antes e depois de serem submetidos à exposição em câmara de UV foram avaliadas por ensaios de resistência à tração e resistência ao impacto Izod. Os resultados obtidos na 1ª etapa deste trabalho indicaram aumento nos valores de módulo de elasticidade de todos os compósitos, em relação à blenda pura. Destacam-se as composições com 5% e 10% em massa de sílica coloidal, que apresentaram aumentos de até 115% nos valores de módulo de elasticidade, sem perdas significativas em resistência à tração, alongamento e resistência ao impacto, quando comparadas à fase matriz. Na 2ª etapa, a partir de 20 dias de exposição, todas as composições (blendas e compósitos) apresentam redução nas propriedades mecânicas em função do aumento do tempo de exposição à radiação UV. Na 3ª etapa, independente do tipo ou teor de carga presente na blenda, todas as composições apresentaram índices de biodegradabilidade, depois de 120 dias, de 40 a 60%, devido à prévia exposição à radiação UV.

MR Anfórico (MR-A) 09/05/2016

Cada vez que se realice un nuevo estudio anfórico se publique el porcentaje de borde conservado de cada ejemplar o el porcentaje medio por tipo. De esa forma se podrán incorporar dichos datos ampliando el grado de fiabilidad de los diferentes tipos. La tabla se denominará “MR Anfórico (MR-A)” seguido de la fecha de actualización que indicará la versión en la que nos encontramos. La tabla actualizada se irá publicando en el Repositorio Institucional de la Universidad de Alicante (RUA) y habrá de ser buscada mediante el término “MR Anfórico (MR-A)”.

Spectroscopie Raman de fibres électrofilées : développement de méthodes et application aux fibres individuelles

L’électrofilage est une technique de mise en œuvre efficace et versatile qui permet la production de fibres continues d’un diamètre typique de quelques centaines de nanomètres à partir de l’application d’un haut voltage sur une solution concentrée de polymères enchevêtrés. L’évaporation extrêmement rapide du solvant et les forces d’élongation impliquées dans la formation de ces fibres leur confèrent des propriétés hors du commun et très intéressantes pour plusieurs types d’applications, mais dont on commence seulement à effleurer la surface. À cause de leur petite taille, ces matériaux ont longtemps été étudiés uniquement sous forme d’amas de milliers de fibres avec les techniques conventionnelles telles que la spectroscopie infrarouge ou la diffraction des rayons X. Nos connaissances de leur comportement proviennent donc toujours de la convolution des propriétés de l’amas de fibres et des caractéristiques spécifiques de chacune des fibres qui le compose. Les études récentes à l’échelle de la fibre individuelle ont mis en lumière des comportements inhabituels, particulièrement l’augmentation exponentielle du module avec la réduction du diamètre. L’orientation et, de manière plus générale, la structure moléculaire des fibres sont susceptibles d’être à l'origine de ces propriétés, mais d’une manière encore incomprise. L’établissement de relations structure/propriétés claires et l’identification des paramètres qui les influencent représentent des défis d’importance capitale en vue de tirer profit des caractéristiques très particulières des fibres électrofilées. Pour ce faire, il est nécessaire de développer des méthodes plus accessibles et permettant des analyses structurales rapides et approfondies sur une grande quantité de fibres individuelles présentant une large gamme de diamètre. Dans cette thèse, la spectroscopie Raman confocale est utilisée pour l’étude des caractéristiques structurales, telles que l’orientation moléculaire, la cristallinité et le désenchevêtrement, de fibres électrofilées individuelles. En premier lieu, une nouvelle méthodologie de quantification de l’orientation moléculaire par spectroscopie Raman est développée théoriquement dans le but de réduire la complexité expérimentale de la mesure, d’étendre la gamme de matériaux pour lesquels ces analyses sont possibles et d’éliminer les risques d’erreurs par rapport à la méthode conventionnelle. La validité et la portée de cette nouvelle méthode, appelée MPD, est ensuite démontrée expérimentalement. Par la suite, une méthodologie efficace permettant l’étude de caractéristiques structurales à l’échelle de la fibre individuelle par spectroscopie Raman est présentée en utilisant le poly(éthylène téréphtalate) comme système modèle. Les limites de la technique sont exposées et des stratégies expérimentales pour les contourner sont mises de l’avant. Les résultats révèlent une grande variabilité de l'orientation et de la conformation d'une fibre à l'autre, alors que le taux de cristallinité demeure systématiquement faible, démontrant l'importance et la pertinence des études statistiques de fibres individuelles. La présence de chaînes montrant un degré d’enchevêtrement plus faible dans les fibres électrofilées que dans la masse est ensuite démontrée expérimentalement pour la première fois par spectroscopie infrarouge sur des amas de fibres de polystyrène. Les conditions d'électrofilage favorisant ce phénomène structural, qui est soupçonné d’influencer grandement les propriétés des fibres, sont identifiées. Finalement, l’ensemble des méthodologies développées sont appliquées sur des fibres individuelles de polystyrène pour l’étude approfondie de l’orientation et du désenchevêtrement sur une large gamme de diamètres et pour une grande quantité de fibres. Cette dernière étude permet l’établissement de la première relation structure/propriétés de ces matériaux, à l’échelle individuelle, en montrant clairement le lien entre l’orientation moléculaire, le désenchevêtrement et le module d'élasticité des fibres.

Spectroscopie Raman de fibres électrofilées : développement de méthodes et application aux fibres individuelles

L’électrofilage est une technique de mise en œuvre efficace et versatile qui permet la production de fibres continues d’un diamètre typique de quelques centaines de nanomètres à partir de l’application d’un haut voltage sur une solution concentrée de polymères enchevêtrés. L’évaporation extrêmement rapide du solvant et les forces d’élongation impliquées dans la formation de ces fibres leur confèrent des propriétés hors du commun et très intéressantes pour plusieurs types d’applications, mais dont on commence seulement à effleurer la surface. À cause de leur petite taille, ces matériaux ont longtemps été étudiés uniquement sous forme d’amas de milliers de fibres avec les techniques conventionnelles telles que la spectroscopie infrarouge ou la diffraction des rayons X. Nos connaissances de leur comportement proviennent donc toujours de la convolution des propriétés de l’amas de fibres et des caractéristiques spécifiques de chacune des fibres qui le compose. Les études récentes à l’échelle de la fibre individuelle ont mis en lumière des comportements inhabituels, particulièrement l’augmentation exponentielle du module avec la réduction du diamètre. L’orientation et, de manière plus générale, la structure moléculaire des fibres sont susceptibles d’être à l'origine de ces propriétés, mais d’une manière encore incomprise. L’établissement de relations structure/propriétés claires et l’identification des paramètres qui les influencent représentent des défis d’importance capitale en vue de tirer profit des caractéristiques très particulières des fibres électrofilées. Pour ce faire, il est nécessaire de développer des méthodes plus accessibles et permettant des analyses structurales rapides et approfondies sur une grande quantité de fibres individuelles présentant une large gamme de diamètre. Dans cette thèse, la spectroscopie Raman confocale est utilisée pour l’étude des caractéristiques structurales, telles que l’orientation moléculaire, la cristallinité et le désenchevêtrement, de fibres électrofilées individuelles. En premier lieu, une nouvelle méthodologie de quantification de l’orientation moléculaire par spectroscopie Raman est développée théoriquement dans le but de réduire la complexité expérimentale de la mesure, d’étendre la gamme de matériaux pour lesquels ces analyses sont possibles et d’éliminer les risques d’erreurs par rapport à la méthode conventionnelle. La validité et la portée de cette nouvelle méthode, appelée MPD, est ensuite démontrée expérimentalement. Par la suite, une méthodologie efficace permettant l’étude de caractéristiques structurales à l’échelle de la fibre individuelle par spectroscopie Raman est présentée en utilisant le poly(éthylène téréphtalate) comme système modèle. Les limites de la technique sont exposées et des stratégies expérimentales pour les contourner sont mises de l’avant. Les résultats révèlent une grande variabilité de l'orientation et de la conformation d'une fibre à l'autre, alors que le taux de cristallinité demeure systématiquement faible, démontrant l'importance et la pertinence des études statistiques de fibres individuelles. La présence de chaînes montrant un degré d’enchevêtrement plus faible dans les fibres électrofilées que dans la masse est ensuite démontrée expérimentalement pour la première fois par spectroscopie infrarouge sur des amas de fibres de polystyrène. Les conditions d'électrofilage favorisant ce phénomène structural, qui est soupçonné d’influencer grandement les propriétés des fibres, sont identifiées. Finalement, l’ensemble des méthodologies développées sont appliquées sur des fibres individuelles de polystyrène pour l’étude approfondie de l’orientation et du désenchevêtrement sur une large gamme de diamètres et pour une grande quantité de fibres. Cette dernière étude permet l’établissement de la première relation structure/propriétés de ces matériaux, à l’échelle individuelle, en montrant clairement le lien entre l’orientation moléculaire, le désenchevêtrement et le module d'élasticité des fibres.

Slowing down a pine invasion despite uncertainty in demography and dispersal

1. Management decisions regarding invasive plants often have to be made quickly and in the face of fragmentary knowledge of their population dynamics. However, recommendations are commonly made on the basis of only a restricted set of parameters. Without addressing uncertainty and variability in model parameters we risk ineffective management, resulting in wasted resources and an escalating problem if early chances to control spread are missed. 2. Using available data for Pinus nigra in ungrazed and grazed grassland and shrubland in New Zealand, we parameterized a stage-structured spread model to calculate invasion wave speed, population growth rate and their sensitivities and elasticities to population parameters. Uncertainty distributions of parameters were used with the model to generate confidence intervals (CI) about the model predictions. 3. Ungrazed grassland environments were most vulnerable to invasion and the highest elasticities and sensitivities of invasion speed were to long-distance dispersal parameters. However, there was overlap between the elasticity and sensitivity CI on juvenile survival, seedling establishment and long-distance dispersal parameters, indicating overlap in their effects on invasion speed. 4. While elasticity of invasion speed to long-distance dispersal was highest in shrubland environments, there was overlap with the CI of elasticity to juvenile survival. In shrubland invasion speed was most sensitive to the probability of establishment, especially when establishment was low. In the grazed environment elasticity and sensitivity of invasion speed to the severity of grazing were consistently highest. Management recommendations based on elasticities and sensitivities depend on the vulnerability of the habitat. 5. Synthesis and applications. Despite considerable uncertainty in demography and dispersal, robust management recommendations emerged from the model. Proportional or absolute reductions in long-distance dispersal, juvenile survival and seedling establishment parameters have the potential to reduce wave speed substantially. Plantations of wind-dispersed invasive conifers should not be sited on exposed sites vulnerable to long-distance dispersal events, and trees in these sites should be removed. Invasion speed can also be reduced by removing seedlings, establishing competitive shrubs and grazing. Incorporating uncertainty into the modelling process increases our confidence in the wide applicability of the management strategies recommended here.

Osmotic dehydration in plant tissues

The primary aim of the thesis is to provide a comprehensive investigation of the osmotic dehydration processes in plant tissue. Effort has been concentrated on the modelling for simulating the processes. Two mathematical models for simulating the mass transfer during osmotic dehydration processes in plant tissues are developed and verified using existing experimental data. Both models are based on the mechanism of diffusion and convection of any mobile material that can transport in plant tissues. The mass balance equation for the transport of each constituent is established separately for intracellular and extra-cellular volumes with taking into account the mass transfer across the cell membrane the intracellular and extra-cellular volumes and the shrinkage of the whole tissue. The contribution from turgor pressure is considered in both models. Model two uses Darcy’s law to build the relation between shrinkage velocity and hydrostatic pressure in each volume because the plant tissue can be considered as the porous medium. Moreover, it has been extended to solve the multi-dimensional problems. A lot of efforts have been made to the parameter study and the sensitivity analyses. The parameters investigated including the concentration of the osmotic solution, diffusion coefficient, permeability of the cell membrane, elastic modulus of the cell wall, critical cell volume etc. The models allow us to quantitatively simulate the time evolution of intracellular and extra-cellular volumes as well as the time evolution of concentrations in each cross-section.