Oligodeoxynucleotide-polypeptide block copolymers

Synthesis and characterization of monodisperse oligonucleotide-polypeptide di- and triblock copolymers are described. These block copolymers are promising building blocks for the formation of defined structures by sequential DNA self-assembly. The oligonucleotide sequences (ODN, 46 bases) obtained from standard solid phase synthesis were designed to form four-arm DNA junctions. The hybridization of the four single stranded oligonucleotides at room temperature to a stable four-arm junction is selective and quantitative. The junctions exhibit good thermal stability as proven by polyacrylamide gel electrophoresis (PAGE) and UV analysis. The second block consists of monodisperse elastin-like polypeptides (ELPs) with a pentapeptide repeat unit of (Val-Pro-Gly-Val-Gly) synthesized by genetic engineering. ODN-ELP diblock copolymers were obtained either by thiol coupling or by activated ester chemistry. Taking advantage of the endgroup control of both components (ODN, ELP), combination of the two different synthetic approaches leads to the synthesis of ODN-ELP-ODN triblock copolymers. Dynamic light scattering measurements of the single components and the synthesized diblock copolymers reveal their monodispersity. Hybridization of four ODN-ELP diblock copolymers carrying the four junction sequences shows quantitative self-assembly. In conclusion, this work provides the first example of the synthesis of perfectly defined ODN-ELP block copolymers and their potential use in DNA self-assembly.

Experimental assessment of environmental decay effects in masonry via non destructive diagnostic techniques and mechanical tests

Environmental decay in porous masonry materials, such as brick and mortar, is a widespread problem concerning both new and historic masonry structures. The decay mechanisms are quite complex dependng upon several interconnected parameters and from the interaction with the specific micro-climate. Materials undergo aesthetical and substantial changes in character but while many studies have been carried out, the mechanical aspect has been largely understudied while it bears true importance from the structural viewpoint. A quantitative assessment of the masonry material degradation and how it affects the load-bearing capacity of masonry structures appears missing. The research work carried out, limiting the attention to brick masonry addresses this issue through an experimental laboratory approach via different integrated testing procedures, both non-destructive and mechanical, together with monitoring methods. Attention was focused on transport of moisture and salts and on the damaging effects caused by the crystallization of two different salts, sodium chloride and sodium sulphate. Many series of masonry specimens, very different in size and purposes were used to track the damage process since its beginning and to monitor its evolution over a number of years Athe same time suitable testing techniques, non-destructive, mini-invasive, analytical, of monitoring, were validated for these purposes. The specimens were exposed to different aggressive agents (in terms of type of salt, of brine concentration, of artificial vs. open-air natural ageing, …), tested by different means (qualitative vs. quantitative, non destructive vs. mechanical testing, punctual vs. wide areas, …), and had different size (1-, 2-, 3-header thick walls, full-scale walls vs. small size specimens, brick columns and triplets vs. small walls, masonry specimens vs. single units of brick and mortar prisms, …). Different advanced testing methods and novel monitoring techniques were applied in an integrated holistic approach, for quantitative assessment of masonry health state.

Functionalization of hyperbranched polycarbosilanes - block copolymers and electrochemistry

Polycarbosilanes are a class of polymers at the interface between organic and inorganic chemistry. They are characterized by a high thermal and chemical inertness and high flexibility, especially pronounced for branched structures. Linear polycarbosilanes are well known as precursors for the preparation of SiCx ceramics. Additionally, more sophisticated architectures like dendrimers, hyperbranched polymers or block copolymers have been the subject of research for more than a decade. The scope of this work was to expand the properties and fields of application for polycarbosilane-containing structures. Thus, the work is divided in two major parts. The first part covers the synthesis and characterization of hyperbranched polycarbosilanes containing organometallic moieties. Hyperbranched poly-carbosilanes were synthesized using hydrosilylation of diallylmethylsilane and methyldiundecenylsilane. The degree of branching for polydiallymethylsilane was determined using standard 1H-NMR spectroscopy. The functional building blocks ferrocenyldimethylsilane and diferrocenylmethylsilane were synthesized which contain an isolated ferrocene unit or two ferrocenes bridged by silicon, respectively. Hyperbranched polycarbosilanes functionalized with ferrocenyl moieties were synthesized by modification of preformed polymers or by copolymerization of AB2 carbosilane monomers with AX-type ferrocenylsilanes. Polymers with Mn = 2500-9000g/mol and ferrocene contents of up to 67wt% were obtained. Electrochemical characterization by cyclic voltammetry revealed that polymers functionalized with isolated ferrocene units showed a single reversible oxidation wave, while voltammograms for polymers functionalized with diferrocenyl silane exhibited two well-separated reversible oxidation-reduction waves. This shows that the polymer bound ferrocenes bridged by silicon are electronically communicating and thus oxidation of the first ferrocene shifts the oxidation potential for the adjacent one. The polymers were utilized successfully for the preparation of modified electrodes with persistent and reproducible electrochemical response in organic solvents as well as in aqueous solution. The presented work has proven that ferrocenyl-functionalized hyperbranched polymers exhibit similar electrochemical properties as the analogous dendrimers. In a further approach it was shown that hyperbranched polymers containing organometallic moieties can be synthesized by polymerization of a new ferrocene-containing AB2 monomer - diallylferrocenylsilane. The second part of this work is dedicated to the preparation of core-functional hyperbranched polycarbosilanes. Low molecular weight ambifunctional molecules were synthesized that contain double bonds for the attachment of a polycarbosilane polymer as well as a second functionality available for further reaction and modification. Reactive vinyl groups in the core molecule allow an efficient attachment of hyperbranched polycarbosilane which was proven by MALDI-ToF and GPC. In combination with slow monomer addition techniques molecular weight and polydispersity of the polymers were controlled successfully. Core-functional polymers were characterized by NMR-spectroscopy, MALDI-ToF and GPC. Polymers with polydispersities <2 and molecular weights up to 5300g/mol were obtained. Transformation of the double bonds of the carbosilane was demonstrated with various silanes using hydrosilylation reaction or hydrogenation. Additionally, the core-functionality was varied resulting in polymers with bromo-, phthalimide-, amine- or azide moieties. Thus, a versatile synthetic strategy was developed that allows the synthesis of tailor-made polymers.A promising approach is the application of the polymer building blocks in copolymer synthesis. Bisglycidolization of amine-functional polycarbosilanes produces macro-initiators that are suitable for the multibranching-ring opening polymerization of glycidol. This experiments lead to the first example of hyperbranched-hyperbranched amphiphilic block copolymers, hb-PG-b-hb-PCS. Furthermore, the implementation of copper-catalyzed cycloaddition between azide-functional polycarbosilane and alkyne-functional poly(ethoxyethyl glycidylether) resulted in linear-hyperbranched block copolymers. The facile removal of acetal protecting groups provided convenient access to lin-PG-b-hb-PCS.

Computer simulation of rod-coil block copolymers and tetrapod,polymer mixtures

In this thesis I present a new coarse-grained model suitable to investigate the phase behavior of rod-coil block copolymers on mesoscopic length scales. In this model the rods are represented by hard spherocylinders, whereas the coil block consists of interconnected beads. The interactions between the constituents are based on local densities. This facilitates an efficient Monte-Carlo sampling of the phase space. I verify the applicability of the model and the simulation approach by means of several examples. I treat pure rod systems and mixtures of rod and coil polymers. Then I append coils to the rods and investigate the role of the different model parameters. Furthermore, I compare different implementations of the model. I prove the capability of the rod-coil block copolymers in our model to exhibit typical micro-phase separated configurations as well as extraordinary phases, such as the wavy lamellar state, percolating structuresrnand clusters. Additionally, I demonstrate the metastability of the observed zigzag phase in our model. A central point of this thesis is the examination of the phase behavior of the rod-coil block copolymers in dependence of different chain lengths and interaction strengths between rods and coil. The observations of these studies are summarized in a phase diagram for rod-coil block copolymers. Furthermore, I validate a stabilization of the smectic phase with increasing coil fraction.rnIn the second part of this work I present a side project in which I derive a model permitting the simulation of tetrapods with and without grafted semiconducting block copolymers. The effect of these polymers is added in an implicit manner by effective interactions between the tetrapods. While the depletion interaction is described in an approximate manner within the Asakura-Oosawa model, the free energy penalty for the brush compression is calculated within the Alexander-de Gennes model. Recent experiments with CdSe tetrapods show that grafted tetrapods are clearly much better dispersed in the polymer matrix than bare tetrapods. My simulations confirm that bare tetrapods tend to aggregate in the matrix of excess polymers, while clustering is significantly reduced after grafting polymer chains to the tetrapods. Finally, I propose a possible extension enabling the simulation of a system with fluctuating volume and demonstrate its basic functionality. This study is originated in a cooperation with an experimental group with the goal to analyze the morphology of these systems in order to find the ideal morphology for hybrid solar cells.

THERMORESPONSIVE PROPERTIES OF GOLD HYBRID NANOPARTICLES OF POLY(DI(ETHYLENE GLYCOL) METHYL ETHER METHACRYLATE) (PDEGMA) AND ITS BLOCK COPOLYMERS WITH DIFFERENT ANCHORING REGIMES

Thermo-responsive materials have been of interest for many years, and have been studied mostly as thermally stimulated drug delivery vehicles. Recently acrylate and methacrylates with pendant ethylene glycol methyl ethers been studied as thermo responsive materials. This work explores thermo response properties of hybrid nanoparticles of one of these methacrylates (DEGMA) and a block copolymer with one of the acrylates (OEGA), with gold nanoparticle cores of different sizes. We were interested in the effects of gold core size, number and type of end groups that anchored the chains to the gold cores, and location of bonding sites on the thermo-response of the polymer. To control the number and location of anchoring groups we using a type of controlled radical polymerization called Reversible Addition Fragmentation Transfer (RAFT) Polymerization. Smaller gold cores did not show the thermo responsive behavior of the polymer but the gold cores did seem to self-assemble. Polymer anchored to larger gold cores did show thermo responsivity. The anchoring end group did not alter the thermoresponsivity but thiol-modified polymers stabilized gold cores less well than chains anchored by dithioester groups, allowing gold cores to grow larger. Use of multiple bonding groups stabilized the gold core. Using block copolymers we tested the effects of number of thiol groups and the distance between them. We observed that the use of multiple anchoring groups on the block copolymer with a sufficiently large gold core did not prevent thermo responsive behavior of the polymer to be detected which allows a new type of thermo-responsive hybrid nanoparticle to be used and studied for new applications.

Biological materials : Part A. tuning LCST of raft copolymers and gold/copolymer hybrid nanoparticles and Part B. biobased nanomaterials

The research described in this dissertation is comprised of two major parts. The first part studied the effects of asymmetric amphiphilic end groups on the thermo-response of diblock copolymers of (oligo/di(ethylene glycol) methyl ether (meth)acrylates, OEGA/DEGMA) and the hybrid nanoparticles of these copolymers with a gold nanoparticle core. Placing the more hydrophilic end group on the more hydrophilic block significantly increased the cloud point compared to a similar copolymer composition with the end group placement reversed. For a given composition, the cloud point was shifted by as much as 28 °C depending on the placement of end groups. This is a much stronger effect than either changing the hydrophilic/hydrophobic block ratio or replacing the hydrophilic acrylate monomer with the equivalent methacrylate monomer. The temperature range of the coil-globule transition was also altered. Binding these diblock copolymers to a gold core decreased the cloud point by 5-15 °C and narrowed the temperature range of the coil-globule transition. The effects were more pronounced when the gold core was bound to the less hydrophilic block. Given the limited numbers of monomers that are approved safe for in vivo use, employing amphiphilic end group placement is a useful tool to tune a thermo-response without otherwise changing the copolymer composition. The second part of the dissertation investigated the production of value-added nanomaterials from two biorefinery “wastes”: lignin and peptidoglycan. Different solvents and spinning methods (melt-, wet-, and electro-spinning) were tested to make lignin/cellulose blended and carbonized fibers. Only electro-spinning yielded fibers having a small enough diameter for efficient carbonization ( Peptidoglycan (a bacterial cell wall material) was copolymerized with poly-(3-hydroxybutyrate), a common polyhydroxyalkanoate produced by bacteria with the objective of determining if a useful material could be obtained with a less rigorous work-up on harvesting polyhydroxyalkanoates. The copolyesteramide product having 25 wt.% peptidoglycan from a highly purified peptidoglycan increased thermal stability by 100-200 °C compared to the poly-(3-hydroxybutyrate) control, while a less pure peptidoglycan, harvested from B. megaterium (ATCC 11561), gave a 25-50 °C increase in thermal stability. Both copolymers absorbed more moisture than pure poly-(3-hydroxybutyrate). The results suggest that a less rigorously harvested and purified polyhydroxyalkanoate might be useful for some applications.

Transition from nerve stimulator to sonographically guided axillary brachial plexus anesthesia in hand surgery: block quality and patient satisfaction during the transition period

OBJECTIVES Sonographic guidance for peripheral nerve anesthesia has proven increasingly successful in clinical practice; however, fears that a change to sonographically guided regional anesthesia may impair the block quality and operating room work flow persist in certain units. In this retrospective cohort study, block quality and patient satisfaction during the transition period from nerve stimulator to sonographic guidance for axillary brachial plexus anesthesia in a tertiary referral center were investigated. METHODS Anesthesia records of all patients who had elective surgery of the wrist or hand during the transition time (September 1, 2006-August 25, 2007) were reviewed for block success, placement time, anesthesiologist training level, local anesthetic volume, and requirement of additional analgesics. Postoperative records were reviewed, and patient satisfaction was assessed by telephone interviews in matched subgroups. RESULTS Of 415 blocks, 341 were sonographically guided, and 74 were nerve stimulator guided. Sonographically guided blocks were mostly performed by novices, whereas nerve stimulator-guided blocks were performed by advanced users (72.3% versus 14%; P < .001). Block performance times and success rates were similar in both groups. In sonographically guided blocks, significantly less local anesthetics were applied compared to nerve stimulator-guided blocks (mean ± SD, 36.1 ± 7.1 versus 43.9 ± 6.1 mL; P< .001), and less opioids were required (fentanyl, 66.1 ± 30 versus 90 ± 62 μg; P< .001). Interviewed patients reported significantly less procedure-related discomfort, pain, and prolonged procedure time when block placement was sonographically guided (2% versus 20%; P = .002). CONCLUSIONS Transition from nerve stimulator to sonographic guidance for axillary brachial plexus blocks did not change block performance times or success rates. Patient satisfaction was improved even during the early institutional transition period.

Place of Work and Place of Residence: Informal Hiring Networks and Labor Market Outcomes

We use a novel dataset and research design to empirically detect the effect of social interactions among neighbors on labor market outcomes. Specifically, using Census data that characterize residential and employment locations down to the city block, we examine whether individuals residing in the same block are more likely to work together than individuals in nearby but not identical blocks. We find significant evidence of social interactions operating at the block level: residing on the same versus nearby blocks increases the probability of working together by over 33 percent. The results also indicate that this referral effect is stronger when individuals are similar in sociodemographic characteristics (e.g., both have children of similar ages) and when at least one individual is well attached to the labor market. These findings are robust across various specifications intended to address concerns related to sorting and reverse causation. Further, having determined the characteristics of a pair of individuals that lead to an especially strong referral effect, we provide evidence that the increased availability of neighborhood referrals has a significant impact on a wide range of labor market outcomes including employment and wages.

Numerical analysis of mixe-mode fracture of brickwork masonry with embedded discontinuity elements

One of the common pathologies of brickwork masonry structural elements and walls is the cracking associated with the differential settlements and/or excessive deflections of the slabs along the life of the structure. The scarce capacity of the masonry in order to accompany the structural elements that surround it, such as floors, beams or foundations, in their movements makes the brickwork masonry to be an element that frequently presents this kind of problem. This problem is a fracture problem, where the wall is cracked under mixed mode fracture: tensile and shear stresses combination, under static loading. Consequently, it is necessary to advance in the simulation and prediction of brickwork masonry mechanical behaviour under tensile and shear loading. The quasi-brittle behaviour of the brickwork masonry can be studied using the cohesive crack model whose application to other quasibrittle materials like concrete has traditionally provided very satisfactory results.

Experimental and Analytical Study of Masonry Infill Reinforced Concrete Frames Retrofitted with Steel Braces

In the present work a seismic retrofitting technique is proposed for masonry infilled reinforced concrete frames based on the replacement of infill panels by K-bracing with vertical shear link. The performance of this technique is evaluated through experimental tests. A simplified numerical model for structural damage evaluation is also formulated according to the notions and principles of continuum damage mechanics. The proposed model is calibrated with the experimental results. The experimental results have shown an excellent energy dissipation capacity with the proposed technique. Likewise, the numerical predictions with the proposed model are in good agreement with experimental results.

Fundamentos constructivos de las fortificaciones fronterizas entre las coronas de Castilla y Aragón de los siglos XII al XV en la actual provincia de Soria

La tesis doctoral desarrolla una investigación original, dentro del marco disciplinario de la historia de la construcción, sobre los fundamentos constructivos de las fortificaciones bajomedievales fronterizas entre las Coronas de Castilla y Aragón en la actual provincia de Soria. En el título de la tesis ya queda expresado el objeto fundamental y fundacional, así como el ámbito temporal —desde la reconquista del oriente soriano por parte de Alfonso I el Batallador a principios del siglo XII hasta la unificación de las coronas hispánicas en el siglo XV bajo el común mandato de los Reyes Católicos— y la extensión territorial que delimita la investigación: aquéllas comarcas castellanas lindantes con Aragón pertenecientes a la actual provincia de Soria. Durante este período bajomedieval se produjeron una serie de enfrentamientos fronterizos que obligó a fortificar la frontera y las vías de comunicación entre ambas coronas. La falta de estudios de conjunto de estas fortificaciones entendiéndolas como participantes en un sistema fortificado ha constituido la justificación de la investigación, que se realiza en varios niveles de análisis: territorial, histórico, arquitectónico, poliorcético y constructivo. Así mismo, se ha detectado cierta falta de rigor acompañada de inexactitudes en las consideraciones constructivas publicadas sobre algunas de las fortificaciones del ámbito de estudio, lo que ha provocado errores en su datación al no más haber elementos de corte artístico o estilístico que marquen indudablemente la pertenencia a una época. En la tesis se ponen en duda las dataciones tradicionalmente aceptadas planteando la hipótesis que da pie a la investigación: ante la falta de elementos artísticos o estilísticos en unos sobrios edificios eminentemente funcionales es posible establecer con suficiente aproximación la fecha de construcción en base a criterios constructivos una vez formada una clasificación cronotipológica de cada técnica constructiva. La hipótesis, por lo tanto, plantea un objetivo principal —el estudio de la razón constructiva del sistema fortificado fronterizo— desarrollado en una serie de objetivos específicos cuya consecución programa los sucesivos niveles de análisis: - Conocer y detallar los elementos históricos que originaron los enfrentamientos entre las Coronas de Castilla y Aragón y su desarrollo mediante herramientas historiográficas y analizar las características naturales del territorio en litigio mediante instrumentos cartográficos. - Conocer y analizar los tipos arquitectónicos y las tradiciones constructivas empleadas en las construcciones castrenses en el ámbito temporal en que se enmarca la investigación. - Localizar, documentar y seleccionar para su análisis las fortalezas y construcciones militares erigidas durante dichas luchas fronterizas en la actual provincia de Soria a través del trabajo de campo y métodos cartográficos y bibliográficos. - Realizar un estudio general sobre el sistema fortificado a escala territorial - Investigar la tipología arquitectónica, poliorcética y constructiva del conjunto de estas fortificaciones bajomedievales fronterizas. - Analizar los fundamentos constructivos de los casos de estudio seleccionados entre estas construcciones y caracterizarlas en cuanto al material, elementos, sistemas y procesos constructivos. - Ordenar la información histórica dispersa y corregir errores para hacer una base sobre la que establecer un discurso histórico de cada caso de estudio. - Comparar y relacionar las técnicas constructivas empleadas en estas fortalezas con los utilizados en el mismo ámbito temporal. - Difundir para su debate los resultados de la investigación por los foros científicos habituales. El método empleado combina los trabajos de gabinete con una intensa labor de campo, en la que se han documentado cincuenta fortificaciones y se han redactado sus correspondientes fichas de toma de datos. La recopilación de datos se ha incluido en una base de datos que incluye aspectos generales, tipológicos, constructivos y bibliográficos básicos del conjunto, a modo de inventario, de fortificaciones de la provincia. Las fortificaciones seleccionadas se agrupan según una clasificación tipológica y constructiva que marca las líneas de estudio posteriores. Se desarrolla un capítulo de antecedentes en el que se estudia la historia de la construcción fortificada medieval tanto en Europa como en España analizando la evolución de los tipos arquitectónicos y las múltiples influencias culturales que surcaron el Mediterráneo desde el Oriente cruzado e islámico al Poniente donde se desarrollaba la empresa reconquistadora que mantuvo en estado de guerra continuo a la Península Ibérica durante ochocientos años. El análisis del territorio como contenedor del hecho fortificado revela que hay una relación íntima entre la ubicación de las fortificaciones y las formas naturales que definen las vías de comunicación entre los valles del Duero, del Ebro y del Tajo. En efecto, el ámbito de estudio ha supuesto desde la Antigüedad un territorio de paso fundamental en la articulación de las comunicaciones en la Península Ibérica. Este carácter de paso más que de frontera explica las inquietudes y la preocupación por su control tanto por Roma como por el califato cordobés como por los reinos cristianos medievales. El análisis de los elementos históricos se complementa con el estudio detallado de los enfrentamientos fronterizos entre Castilla y Aragón así como los aspectos sociales y políticos que provocaron la fortificación como sistema de definición de la frontera y de organización espacial, jurisdiccional, social y administrativa del territorio. La arquitectura fortificada es esencialmente funcional: su cometido es la defensa. En este sentido, tras un estudio morfológico de los castillos seleccionados se realiza un extenso análisis poliorcético de sus elementos, investigando su origen y aplicación para servir también de parámetros de datación. Siendo el objeto inaugural de la tesis el estudio de los fundamentos constructivos, se explican los distintos materiales de construcción empleados y se agrupan las fábricas de las fortificaciones seleccionadas en dos grandes grupos constructivos: las fábricas aparejadas y las fábricas encofradas. Se han destacado y estudiado la evolución histórica y la tipología y mensiología constructiva de tres técnicas destacadas: el uso del ladrillo, la tapia de cal y canto o mampostería encofrada y la tapia de tierra. Para el estudio de la componente histórica y de la dimensión constructiva de cada técnica ha sido necesario documentar numerosos casos tanto en el ámbito de estudio como en la Península Ibérica con el fin de establecer grupos cronotipológicos constructivos entre los que poder ubicar las fábricas de estas técnicas presentes en el ámbito de estudio. Se ha observado una evolución dimensional de las fábricas de tapia que es más evidente en las hispanomusulmanas al modularse en codos pero que también se advierte significativamente en las cristianas bajomedievales. De cada una de las técnicas analizadas se ha seleccionado un caso de estudio singular y representativo. El castillo de Arcos de Jalón es un ejemplo significativo del empleo de la fábrica mixta de mampostería con verdugadas de ladrillo, así como las murallas de la ciudad fortificada de Peñalcázar lo es de la fábrica de mampostería encofrada y el castillo de Serón de Nágima constituye un caso característico y principal de la utilización de la tapia de tierra en la arquitectura militar bajomedieval. Cada uno de estos tres casos de estudios se examina bajo los mismos cuatro niveles anteriormente mencionados: territorial, histórico, arquitectónico y defensivo y constructivo. El sistemático método de estudio ha facilitado el orden en la investigación y la obtención de unos resultados y conclusiones que verifican la hipótesis y cumplen los objetivos marcados al comienzo. Se ha revisado la datación en la construcción de las fortificaciones analizadas mediante el estudio cronotipológico de sus fábricas, pudiendo trasladarse el método a otros sistemas fortificados. La tesis abre, finalmente, dos vías principales de investigación encaminadas a completar el estudio del sistema fortificado fronterizo bajomedieval en la raya oriental soriana de Castilla: la caracterización y datación por métodos físico-químicos de las muestras de piezas de madera de construcción que se conservan embebidas en las fábricas y la búsqueda documental y archivística que pueda revelar nuevos datos respecto a la fundación, reparación, venta o cualquier aspecto económico, legislativo, organizativo o administrativo relativo a las fortificaciones en documentos coetáneos. ABSTRACT The doctoral thesis develops an original research, held in the field of the Construction History, about the constructive reason of the frontier fortifications in the Late Middle Age between the Crowns of Castile and Aragón in the actual province of Soria, Spain. In the title is expressed the main objective, and also the temporal scope —from the reconquest in the 12th Century by Alfonso the First of Aragón to the unification under the common kingdom of the Catholic Kings— and the territorial extension that the research delimits: those Castilian regions in the border with Aragón in the actual province of Soria. During this period, a series of border wars were been, and this is the reason for the fortification of the border line and the main roads between both Crowns. The lack of studies of these fortifications as participants in a fortified system is the justification of the research. There is several analysis levels: territorial, historical, architectonic, defensive and constructive. Likewise, there is a lack of strictness and inaccuracy in the constructive items in the publications about several fortifications of this study field. This aspect has caused mistakes in the dating because there is neither artistic nor stylistic elements which determines a epoch. The traditionally accepted datings are challenged. An hypothesis is formulated: in the absence of artistic or stylistic elements in a sober and functional buildings is possible to date the time of construction with sufficiently approximation based on construction criteria once formed a cronotypologic classification of each building technique. The hypothesis, therefore, propose a main aim: the study of the constructive reason of the fortified border system. This aim is developed in a series of specifically targets whose achievement programs the analysis levels: - To know and to detail the historical elements which started the wars between Castile and Aragon and its development using historiographical tools, and to analyze the natural characteristic of the territory through cartographical tools. - To understand and to analyze the different architectural types and the building traditions employed in the military buildings in the time researched. - To locate, to document, and to select for their analysis the fortresses and military constructions erected during these border wars in the actual province of Soria through fieldwork and bibliographical and cartographical methods. - To conduct a general study on the fortified system in territorial scale. - To research the architectural, constructive and defensive typology of the system of these border late medieval fortifications. - To analyze the construction logic of the selected case studies and to characterize in the items of material, elements, systems and construction processes. - To sort scattered historical information and to correct mistakes to make a base by which to establish a historic speech of each case study. - To compare and to relate the construction techniques employed in these fortresses with those used in the same time range . - To spread for discussion the research results in the usual scientists forums. The method combines the destock work with an intense fieldwork. Fifty fortifications have been documented and it has written their corresponding data collection card. Data collection has been included in a database that includes general aspects, typological, constructive and basic bibliographical data, as an inventory of fortifications in the province. The selected fortifications are grouped according to a typological and constructive classification which lead the lines of the later study. There is a chapter for the antecedents in which the history of the medieval fortified construction in Europe and in Spain is studied by analyzing the evolution of architectural types and the many cultural influences along the opposite seasides of the Mediterranean Sea, from the Islamic and Crusader East to the Iberian Peninsula in where there were a long and continuous war during eight hundred years. The territory is analyzed as a container of fortifications. This analysis reveals that there is an intimate relationship between the location of the fortifications and the natural forms that define the communication roads between the Duero, Ebro and Tajo valleys. Indeed, the study area has been a cross-territory from ancient times more than a frontierterritory. This communication character explains the concerns about its control both by Rome and by the Muslims of Córdoba as medieval Christian kingdoms. The analysis of historical elements is supplemented by detailed study of border war between Castile and Aragon and the social and political issues that led to the fortification as border definition system and spatial, jurisdictional, social and administrative planning. The fortified architecture is essentially functional: it is responsible for defense. In this sense, after a morphological study of selected castles is performed an extensive analysis of its defensive elements, investigating its origin and application. This analisis serves for the definition of parameters for dating. The purpose of the thesis is the study of the constructive logic. First, various building materials are explained. Then, masonry is grouped into two major constructive groups: rigged masonry and formwork masonry. The historical evolution and the constructive typology and mensiology are studied for each one of the three main techniques: the use of brickwork, the mortar wall and rammed-earth. Many case studies have been documented along the Iberian Peninsula and also in the study area. As conclusion, there is a dimensional evolution of the rammed-earth walls. This evolution is more evident into the Muslim masonry than in the late medieval walls: the reason is the use of the cubit as module. From each of the techniques discussed, a singular and representative case of study has been selected. The castle of Arcos de Jalon is a significant example of mix masonry of stone and brick rows. The walled city of Peñalcázar is built with masonry formwork. Serón de Nágima castle, at last, is a typical and main case of the use of the rammedearth wall of late medieval military architecture. Each of these three case studies were examined under the same four analysis levels above mentioned: territorial, historical, architectural and defensive and constructive. The systematic method of study has facilitated the order in the research and the obtaining of results and conclusions that verify the hypotheses and achieve the research objectives. Dating of the fortifications construction has been revised by studying the cronotypological issues of its masonry. The method can be transferred to the study of other fortified systems. Finally, the thesis describes two main research new ways aimed at completing the study of the late medieval fortified border of Castile in the actual province of Soria. The first of them is the characterization and datig by physicochemical methods the sample pieces of wood construction preserved embedded in the masonry. The second research way is the investigation of the documents in archives that may reveal new information about the foundation, repair, sale or any aspect to economic, legal, organizational or administrative concerning fortifications in contemporary documents.

Testing the performance of a green wall system on an experimental building in the summer

It is known that a green wall brings some advantages to a building. It constitutes a barrier against solar radiation, thus decreasing and delaying the incoming heat flux. The aim of this study is to quantify such advantages through analytical comparison between two facades, a vegetal facade and a conventional facade. Both were highly insulated (U-value = 0.3 W/m2K) and installed facing south on the same building in the central territory of Spain. In order to compare their thermal trend, a series of sensors were used to register superficial and indoor air temperature. The work was carried out between 17th August 2012 and 1st October 2012, with a temperature range of 12°C-36°C and a maximum horizontal radiation of 1020 W/m2. Results show that the indoor temperature of the green wall module was lower than the other. Besides, comparing superficial outdoor and indoor temperatures of the two walls to outdoor air temperatures, it was noticed that, due to the shading plants, the green wall superficial temperature was 5 °C lower on the facade, while the bare wall temperature was 15 °C higher. The living wall module temperature was 1.6 °C lower than the outdoor, while the values of the conventional one were similar to the outdoor air temperature.

Assessing construction and demolition waste on masonry works to avoid future generation

The difficulty of dealing with construction and demolition waste (CDW) on construction sites is not new and continues to be a significant environmental problem. Currently the CDW collection system in Spain is done in a decentralized manner by each sub-contracted company, being necessary to implement effective waste management measures ensuring a correct management and minimization. During the last years several measures have been launched in order to improve and encourage the reuse and recycling of CDW. A widespread solution for CDW recovery is using them as a landscaping aggregate or for road bases and sub-bases. However, measures encouraging onsite prevention still need to be enhanced. This paper studies the major work stage generating CDW and analyses the categories of CDW produced during its execution. For this, several real building sites have been analysed in order to quantify the estimation of CDW generated. Results of this study show that a significant contributor to the CDW generation on building construction sites in Spain are the masonry works. Finally, a Best Practices Manual (BPM) is proposed containing several strategies on masonry works aimed not only at CDW prevention, but also at improving their management and minimization. The use of this BPM together with the Study and Plan of CDW management --required by law--, promotes the environmental management of the company, favouring the cohesion of the construction process organization at all stages giving rise to establishing responsibilities in the field of waste and providing a greater control over the process. Keywords: construction and demolition waste, management, masonry works, good practice measures, prevention.

Design of a Semi-analytical Method to Describe Plasma-Wall Interactions

Electric probes are objects immersed in the plasma with sharp boundaries which collect of emit charged particles. Consequently, the nearby plasma evolves under abrupt imposed and/or naturally emerging conditions. There could be localized currents, different time scales for plasma species evolution, charge separation and absorbing-emitting walls. The traditional numerical schemes based on differences often transform these disparate boundary conditions into computational singularities. This is the case of models using advection-diffusion differential equations with source-sink terms (also called Fokker-Planck equations). These equations are used in both, fluid and kinetic descriptions, to obtain the distribution functions or the density for each plasma species close to the boundaries. We present a resolution method grounded on an integral advancing scheme by using approximate Green's functions, also called short-time propagators. All the integrals, as a path integration process, are numerically calculated, what states a robust grid-free computational integral method, which is unconditionally stable for any time step. Hence, the sharp boundary conditions, as the current emission from a wall, can be treated during the short-time regime providing solutions that works as if they were known for each time step analytically. The form of the propagator (typically a multivariate Gaussian) is not unique and it can be adjusted during the advancing scheme to preserve the conserved quantities of the problem. The effects of the electric or magnetic fields can be incorporated into the iterative algorithm. The method allows smooth transitions of the evolving solutions even when abrupt discontinuities are present. In this work it is proposed a procedure to incorporate, for the very first time, the boundary conditions in the numerical integral scheme. This numerical scheme is applied to model the plasma bulk interaction with a charge-emitting electrode, dealing with fluid diffusion equations combined with Poisson equation self-consistently. It has been checked the stability of this computational method under any number of iterations, even for advancing in time electrons and ions having different time scales. This work establishes the basis to deal in future work with problems related to plasma thrusters or emissive probes in electromagnetic fields.

Separation of the arterial wall from blood contact using hydrogel barriers reduces intimal thickening after balloon injury in the rat: The roles of medial and luminal factors in arterial healing

The objective of this study was to clarify the relative roles of medial versus luminal factors in the induction of thickening of the arterial intima after balloon angioplasty injury. Platelet-derived growth factor (PDGF) and thrombin, both associated with thrombosis, and basic fibroblast growth factor (bFGF), stored in the arterial wall, have been implicated in this process. To unequivocally isolate the media from luminally derived factors, we used a 20-μm thick hydrogel barrier that adhered firmly to the arterial wall to block thrombus deposition after balloon-induced injury of the carotid artery of the rat. Thrombosis, bFGF mobilization, medial repopulation, and intimal thickening were measured. Blockade of postinjury arterial contact with blood prevented thrombosis and dramatically inhibited both intimal thickening and endogenous bFGF mobilization. By blocking blood contact on the two time scales of thrombosis and of intimal thickening, and by using local protein release to probe, by reconstitution, the individual roles of PDGF-BB and thrombin, we were able to conclude that a luminally derived factor other than PDGF or thrombin is required for the initiation of cellular events leading to intimal thickening after balloon injury in the rat. We further conclude that a luminally derived factor is required for mobilization of medial bFGF.