THE DESIGN AND SYNTHESIS OF SILOXANE PRECURSORS FOR CHIRAL PERIODIC MESOPOROUS ORGANOSILICA MATERIALS

The development of cost-effective and reliable methods for the synthesis and separation of asymmetric compounds is paramount in helping to meet society’s ever-growing demand for chiral small molecules. Of these methods, chiral heterogeneous supports are particularly appealing as they allow for the reuse of the chiral source. One such support, based on the synergy between chiral organic units and structurally stable inorganic silicon scaffolds are periodic mesoporous organosilicas (PMOs). In the work described herein, I examine some of the factors governing the transmission of chirality between chiral dopants and prochiral bulk phases in chiral PMO materials. In particular, the exploration of 1,1’-binaphthalene-bridged chiral dopants with a focus on the point of attachment into the materials. Moreover, the effects of ordering in the materials are examined and reveal that chirality transfer is more facile in materials with molecular-scale order then those containing amorphous walls. Secondly, the issues surrounding the synthesis and purification of aryl-triethoxysilanes as siloxane precursors are addressed. Both the introduction of a two-carbon linker and the direct attachment of allyl and mixed allyldiethoxysilane species are explored. This work demonstrates that allyldiethoxysilanes are ideal, in that they are stable enough to permit facile synthesis, while still being able to hydrolyze completely to produce well-ordered materials. Lastly, the production of new bulk phases for chiral PMO materials is examined by introducing new prochiral nitrogen-containing siloxane precursors. Biphenyldiamine and bipyridine-bridged siloxane precursors are readily synthesized on reasonable scales. Their use as the bulk siloxane precursor in the production of PMO materials however, is precluded by insufficient gelation and additional siloxane precursors are necessary for the production of ordered materials. In addition to the research detailed above that forms the body of this thesis, two short works are appended. The first details the production of polythiophene assemblies mediated through coordination nanospaces, while the second explores the production of N-heterocyclic carbene functionalized gold nanoparticles through ligand exchange.

Advertisement and society in graphic magazine: La Esfera (1920-1930)

In the first third of the 20th century, Spain entered into modernity thanks to the positive state of its economic, cultural and social domains after the First World War. The objective of this article is to understand the role of artistic advertisements in the transformation of Spanish society that occurred during the decade of the ‘20s. My study of the illustrated magazine La Esfera has revealed that illustrated advertisements spread fashion, fostered sports and outdoors life, created the habit of smoking among women and had an educational influence that was powerful enough to change hygienic practices among children.

Potencial de cambio en las capacidades humanas de los docentes de educación básica en la región socioeducactiva de Tuxtla Gutiérrez, Chiapas, México

La investigación que se presenta fue desarrollada dentro del campo de los estudios regionales y con visión transdisciplinar. Tuvo como objetivo deconstruir conjuntamente con los participantes, las capacidades humanas regionales de nosotros los docentes de educación básica, en nuestros procesos de reflexión entre teoría y práctica, en los que se consideraron las condicionantes estructurales, en niveles macro y micro regionales, con el alcance de haber identificado el potencial de cambio en nuestra praxis de docente como acción ante nuestros alumnos, quienes configuran el tejido social de Tuxtla Gutiérrez. Desde una perspectiva sociocrítica, se tomó como punto de fuga o núcleo la teoría crítica con fundamento filosófico en la escuela de Fráncfort y con una postura epistemológica basada en el construccionismo por la estrecha relación sujeto-objeto en el estudio; por ende se empleó la metodología investigaciónacción a través de diversas técnicas e instrumentos. Los resultados fueron concentrados en categorías que facilitaron su discusión: primeramente con el potencial de cambio, que adquirió significado mediante el desarrollo de las capacidades de reflexión y conciencia del docente; luego se presentaron las capacidades humanas, de nosotros los docentes, en las que destacaron como base de otras, las capacidades de amor, autoestima y compromiso. Posteriormente, se describió la reflexión docente sobre la concepción del beneficio personal hacia el beneficio colectivo. Finalmente, se discutió sobre la proyección de la acción docente dentro de la relación alumno y región. Se concluyó que las capacidades humanas y el potencial de cambio, deconstruidos conjuntamente con los docentes participantes, fueron la respuesta del proceso investigativo en un determinado tiempo y espacio, como posibilidades de acción docente hacia la tan deseada transformación socioeducativa regional.

Diagnóstico del rendimiento académico de estudiantes de una escuela de educación superior en México

El objetivo del artículo es realizar un diagnóstico sobre la percepción de los factores que intervienen en el rendimiento académico de los estudiantes de cinco carreras universitarias en una escuela de educación superior en México, para así reconocer las áreas de oportunidad que permitan sugerir políticas y estrategias para elevar su rendimiento. Se utilizó una muestra de 1651 estudiantes, se obtuvieron los datos a partir de un cuestionario con treinta preguntas que estudian la percepción del rendimiento académico en escala tipo Likert. Se realizó un análisis factorial exploratorio que permitiera reducir los datos, facilitar la interpretación y validar el instrumento. Se identificaron tres factores: a) el rol de los profesores, b) la evaluación y c) la motivación de los estudiantes. Se llevó a cabo un análisis comparativo por carrera. Se encontró que los estudiantes perciben que la mayoría de los maestros no se preocupan por la condición de los jóvenes en situación de reprobación. Además, casi no motivan y carecen de expresiones de sentimientos de orgullo por los logros académicos de los estudiantes. La mitad de los participantes piensa que los docentes no cubren el temario en su totalidad. Se detectó que los estudiantes poseen una alta motivación siendo esto positivo porque son alumnos dedicados y responsables. Se concluye realizando una serie de sugerencias y explicando las implicaciones que tiene este trabajo para las instituciones de educación superior.

Determinantes del desarrollo económico local del municipio de Belén de los Andaquíes, departamento del Caquetá.

La falta de claridad en relación a los modelos de desarrollo pertinentes para esta región amazónica, frente a los actuales escenarios de globalización, y la falta de voluntad política, han profundizado problemáticas estructurales (violencia, desempleo, pobreza, desigualdad, entre otros), reflejadas en sus bajos niveles de desarrollo; es así, como durante la historia, el departamento del Caquetá y por tanto sus municipios, se ha caracterizado por afrontar sus procesos de desarrollo en una forma espontánea y desordenada, con falencias en su planeación y mediada por iniciativa propia de los actores institucionales o impuesto por planes elaborados a nivel central o de instancias internacionales.

Estado poblacional del ganado Reyna en Nicaragua: distribución, manejo, producción y cualidades

El presente estudio se realizó en colaboración con el organismo italiano CROCEVIA, y en él se pretendió determinar el nivel poblacional, distribución geográfica, elementos de manejo, utilización y características del ganado criollo Reyna. Se determinó que esta raza está presente en once de los dieciséis departamentos del país, al canzando una población total de 1 963 cabezas, de las cuales 1184 corresponden al hato puro y 779 al hato cruzado, siendo los departamentos de Rivas y Boaco los que alcanzaron la mayor población de hato puro. Los sistemas donde se explota esta raza, principalmente son de doble propósito, con alimentación basada en el pastoreo, que en algunos casos se acompaña de suplementación durante el ordeño. Se identificaron 20 especies de pastos en las fincas donde se explota esta raza. La producción de leche en el hato puro se obtiene por ordeño doble o sencillo alcanzando en el primer caso niveles de cuatro a cinco kg en invierno y de cinco a seis kg en verano, y cuando se realiza un solo ordeño, 4.5 kg y 5.5 kg en invierno y verano respectivamente. En el hato cruzado prevalece un solo ordeño con producciones que oscilan entre cuatro y 11 kg en invierno y de tres a 13 kg en verano. De los cruces raciales en los que participa el Reyna se registraron 23, con el predominio de media sangre y un cuarto Reyna en combinación con seis razas. En relación a sus cualidades se registraron 18 bondades y siete defectos señalados por los productores

Hydrothermal carbonization in the synthesis of sustainable porous carbon materials

Carbon materials are found versatile and applicable in wide range of applications. During the recent years research of carbon materials has focussed on the search of environmentally friendly, sustainable, renewable and low-cost starting material sources as well as simple cost-efficient synthesis techniques. As an alternative synthesis technique in the production of carbon materials hydrothermal carbonization (HTC) has shown a great potential. Depending on the application HTC can be performed as such or as a pretreatment technique. This technique allows synthesis of carbon materials i.e. hydrochars in closed vessel in the presence of water and self-generated pressure at relatively low temperatures (180-250 ˚C). As in many applications well developed porosity and heteroatom distribution are in a key role. Therefore in this study different techniques e.g. varying feedstock, templating and post-treatment in order to introduce these properties to the hydrochars structure were performed. Simple monosaccharides i.e. fructose or glucose and more complex compounds such as cellulose and sludge were performed as starting materials. Addition of secondary precursor e.g. thiophenecarboxaldehyde and ovalbumin was successfully exploited in order to alter heteroatom content. It was shown that well-developed porosity (SBET 550 m2/g) can be achieved via one-pot approach (i.e. exploitation of salt mixture) without conventionally used post-carbonization step. Nitrogen-enriched hydrochars indicated significant Pb(II) and Cr(VI) removal efficiency of 240 mg/g and 68 mg/g respectively. Sulphur addition into carbon network was not found to have enhancing effect on the adsorption of methylene blue or change acidity of the carbon material. However, these hydrochars were found to remove 99.9 % methylene blue and adsorption efficiency of these hydrochars remained over 90 % even after regeneration. In addition to water treatment application N-rich high temperature treated carbon materials were proven applicable as electrocatalyst and electrocatalyst support. Hydrothermal carbonization was shown to be workable technique for the production of carbon materials with variable physico-chemical properties and therefore hydrochars could be applied in several different applications e.g. as alternative low-cost adsorbent for pollutant removal from water.

High-Throughput Prediction of Acacia and Eucalypt Lignin Syringyl/Guaiacyl Content Using FT-Raman Spectroscopy and Partial Least Squares Modeling

High-throughput techniques are necessary to efficiently screen potential lignocellulosic feedstocks for the production of renewable fuels, chemicals, and bio-based materials, thereby reducing experimental time and expense while supplanting tedious, destructive methods. The ratio of lignin syringyl (S) to guaiacyl (G) monomers has been routinely quantified as a way to probe biomass recalcitrance. Mid-infrared and Raman spectroscopy have been demonstrated to produce robust partial least squares models for the prediction of lignin S/G ratios in a diverse group of Acacia and eucalypt trees. The most accurate Raman model has now been used to predict the S/G ratio from 269 unknown Acacia and eucalypt feedstocks. This study demonstrates the application of a partial least squares model composed of Raman spectral data and lignin S/G ratios measured using pyrolysis/molecular beam mass spectrometry (pyMBMS) for the prediction of S/G ratios in an unknown data set. The predicted S/G ratios calculated by the model were averaged according to plant species, and the means were not found to differ from the pyMBMS ratios when evaluating the mean values of each method within the 95 % confidence interval. Pairwise comparisons within each data set were employed to assess statistical differences between each biomass species. While some pairwise appraisals failed to differentiate between species, Acacias, in both data sets, clearly display significant differences in their S/G composition which distinguish them from eucalypts. This research shows the power of using Raman spectroscopy to supplant tedious, destructive methods for the evaluation of the lignin S/G ratio of diverse plant biomass materials. © 2015, The Author(s).

Reconstructability of 3-Dimensional Upper Ocean Circulation from SWOT Sea Surface Height Measurements

Utilizing the framework of effective surface quasi-geostrophic (eSQG) theory, we explored the potential of reconstructing the 3D upper ocean circulation structures, including the balanced vertical velocity (w) field, from high-resolution sea surface height (SSH) data of the planned SWOT satellite mission. Specifically, we utilized the 1/30°, submesoscale-resolving, OFES model output and subjected it through the SWOT simulator that generates the along-swath SSH data with expected measurement errors. Focusing on the Kuroshio Extension region in the North Pacific where regional Rossby numbers range from 0.22 to 0.32, we found that the eSQG dynamics constitutes an effective framework for reconstructing the 3D upper ocean circulation field. Using the modeled SSH data as input, the eSQG-reconstructed relative vorticity (ζ) and w fields are found to reach a correlation of 0.7–0.9 and 0.6–0.7, respectively, in the 1,000m upper ocean when compared to the original model output. Degradation due to the SWOT sampling and measurement errors in the input SSH data for the ζ and w reconstructions is found to be moderate, 5–25% for the 3D ζ field and 15-35% for the 3D w field. There exists a tendency for this degradation ratio to decrease in regions where the regional eddy variability (or Rossby number) increases.

Freie Schulwahl und staatliche Steuerung. Neue Regelungen des Übergangs an weiterführende Schulen

In dem vorliegenden Beitrag werden neuere schulgesetzliche Initiativen erörtert, die u.a. eine Reform des Übertritts aus der Grundschule an weiterführende Schulen beabsichtigen. Diese Bemühungen ordnen sich in die schon lange zu beobachtende Tendenz zur Stärkung der individuellen Rechte von Schülern und Eltern ein, wie sie mit dem Prozeß der Verrechtlichung der Schule in der Bundesrepublik verbunden ist. Eine genauere Betrachtung der entsprechenden Regelungen und einiger dadurch ausgelöster gerichtlicher Konflikte weckt allerdings Zweifel an Voraussetzungen und insbesondere an Ergebnissen der eingeleiteten Politik: Handelt es sich nicht doch um eine versteckte Form der staatlichen Steuerung der Schulwahl? (DIPF/Orig.)

Characterization of 27 microsatellite loci in the European flat oyster Ostrea edulis

The flat oyster Ostrea edulis is native to Europe and populations have been severely depleted by the parasite Bonamia ostreae since the 1980s. Additional genetic markers are required to improve population genetics study and linkage map development for selection for B. ostrea-resistance in this species. Here, we characterized 27 novel microsatellite loci for O. edulis. Number of alleles per locus ranged from 6 to 25 and observed heterozygosity between 0.375 and 1. Null alleles were suggested at a few loci but most loci were in Hardy-Weinberg agreement enabling their reliable use in further population and mapping genetics approaches.

Caracterização biométrica e acúmulo de nutrientes em porta-enxertos de caramboleira cultivada em solução nutritiva

O conhecimento sobre o crescimento e o acúmulo de nutrientes em hipobiotos de caramboleira permite melhor eficiência da adubação na produção de hipobiotos (porta-enxertos). Objetivou-se determinar o crescimento e o acúmulo de nutrientes em hipobiotos de caramboleira cultivada em solução nutritiva. O experimento constituiu de cinco tratamentos, referentes aos tempos de coleta 25; 50; 75; 100 e 125 dias após o transplantio, dispostos em delineamento inteiramente casualizado em seis repetições. As plantas utilizadas foram obtidas de sementes de frutos de caramboleira 'Malásia', cultivadas em vasos com solução nutritiva. Nos diferentes órgãos dos hipobiotos (folhas, caule e raízes), avaliou-se o crescimento e o acúmulo de nutrientes e os índices nutricionais, a cada 25 dias. O ponto de enxertia (6 mm) foi atingido aos 110 dias após o transplantio. A ordem decrescente dos nutrientes acumulados em cada hipobioto produzido é de (em mg por planta): N = 634; K = 368; Ca = 152; Mg = 106; S = 98; P = 88 (em µg por planta) de: Fe = 2.963; Mn = 2.165; B = 722; Zn =780, e Cu = 96. O acúmulo médio de nutrientes é maior nas folhas > caule = raízes. O período de maior exigência de nutrientes pelos hipobiotos é compreendido entre 25-75 dias após o transplantio. As diferentes taxas de acumulação líquida dos nutrientes, nas diferentes partes da caramboleira, nem sempre acompanham a taxa de acumulação de nutrientes do respectivo órgão.

Interventions for dysphagia in acute stroke (Review)

Background It is unclear how dysphagic patients should be fed and treated after acute stroke. Objectives The objective of this review was to assess the effect of different management strategies for dysphagic stroke patients, in particular how and when to feed, whether to supplement nutritional intake, and how and whether to treat dysphagia. Search strategy We searched the Cochrane Stroke Group trials register, Medline, Embase, ISI, and existing review articles.We contacted researchers in the field and equipment manufacturers. Date of the most recent searches: March 1999. Selection criteria Unconfounded truly or quasi randomised controlled trials in dysphagic patients with acute/subacute (within 3 months) stroke. Data collection and analysis Three reviewers independently applied the trial inclusion criteria. Two reviewers assessed trial quality and extracted the data. Main results Percutaneous endoscopic gastrostomy (PEG) versus nasogastric tube (NGT) feeding: two trials (49 patients) suggest that PEG reduces end-of-trial case fatality (Peto Odds Ratio, OR 0.28, 95% CI 0.09 to 0.89) and treatment failures (OR 0.10, 95% CI 0.02 to 0.52), and improves nutritional status, assessed as weight (Weighted Men Difference, WMD +4.1 kg, 95% CI -4.3 to +12.5), mid-arm circumference (WMD +2.2 cm, 95% CI -0.5 to +4.9) or serum albumin (WMD + 7.0 g/l, 95% CI +4.9 to +9.1) as compared with NGT feeding; two larger studies are ongoing. Timing of feeding: no completed trials; one large study is ongoing. Swallowing therapy for dysphagia: two trials (85 patients) suggest that formal swallowing therapy does not significantly reduce end-of-trial dysphagia rates (OR 0.55, 95%CI 0.18 to 1.66). Drug therapy for dysphagia: one trial (17 patients); nifedipine did not alter end-of-trial case fatality or the frequency of dysphagia. Nutritional supplementation: one trial (42 patients) found a non-significant trend to a lower case fatality, and significantly increased energy and protein intake; one large trial is ongoing and data is awaited from two other studies. Fluid supplementation: one trial (20 patients) found that supplementation did not alter the time to resolution of dysphagia. Authors’ conclusions Too few studies have been performed, and these have involved too few patients. PEG feeding may improve outcome and nutrition as compared with NGT feeding. Further research is required to assess how and when patients are fed, and the effect of swallowing or drug therapy on dysphagia.

Search for Higgs Boson Production Beyond the Standard Model Using the Razor Kinematic Variables in pp Collisions at √s=8 TeV and Optimization of Higgs Boson Identification Using a Quantum Annealer

In the first part of this thesis we search for beyond the Standard Model physics through the search for anomalous production of the Higgs boson using the razor kinematic variables. We search for anomalous Higgs boson production using proton-proton collisions at center of mass energy √s=8 TeV collected by the Compact Muon Solenoid experiment at the Large Hadron Collider corresponding to an integrated luminosity of 19.8 fb^-1.

In the second part we present a novel method for using a quantum annealer to train a classifier to recognize events containing a Higgs boson decaying to two photons. We train that classifier using simulated proton-proton collisions at √s=8 TeV producing either a Standard Model Higgs boson decaying to two photons or a non-resonant Standard Model process that produces a two photon final state.

The production mechanisms of the Higgs boson are precisely predicted by the Standard Model based on its association with the mechanism of electroweak symmetry breaking. We measure the yield of Higgs bosons decaying to two photons in kinematic regions predicted to have very little contribution from a Standard Model Higgs boson and search for an excess of events, which would be evidence of either non-standard production or non-standard properties of the Higgs boson. We divide the events into disjoint categories based on kinematic properties and the presence of additional b-quarks produced in the collisions. In each of these disjoint categories, we use the razor kinematic variables to characterize events with topological configurations incompatible with typical configurations found from standard model production of the Higgs boson.

We observe an excess of events with di-photon invariant mass compatible with the Higgs boson mass and localized in a small region of the razor plane. We observe 5 events with a predicted background of 0.54 ± 0.28, which observation has a p-value of 10^-3 and a local significance of 3.35σ. This background prediction comes from 0.48 predicted non-resonant background events and 0.07 predicted SM higgs boson events. We proceed to investigate the properties of this excess, finding that it provides a very compelling peak in the di-photon invariant mass distribution and is physically separated in the razor plane from predicted background. Using another method of measuring the background and significance of the excess, we find a 2.5σ deviation from the Standard Model hypothesis over a broader range of the razor plane.

In the second part of the thesis we transform the problem of training a classifier to distinguish events with a Higgs boson decaying to two photons from events with other sources of photon pairs into the Hamiltonian of a spin system, the ground state of which is the best classifier. We then use a quantum annealer to find the ground state of this Hamiltonian and train the classifier. We find that we are able to do this successfully in less than 400 annealing runs for a problem of median difficulty at the largest problem size considered. The networks trained in this manner exhibit good classification performance, competitive with the more complicated machine learning techniques, and are highly resistant to overtraining. We also find that the nature of the training gives access to additional solutions that can be used to improve the classification performance by up to 1.2% in some regions.