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.

Advanced Nanostructured Electro-Catalysts for Electricity Generation and Biorenewable Alcohol Conversion

In my Ph.D research, a wet chemistry-based organic solution phase reduction method was developed, and was successfully applied in the preparation of a series of advanced electro-catalysts, including 0-dimensional (0-D) Pt, Pd, Au, and Pd-Ni nanoparticles (NPs), 1-D Pt-Fe nanowires (NWs) and 2-D Pd-Fe nanoleaves (NLs), with controlled size, shape, and morphology. These nanostructured catalysts have demonstrated unique electro-catalytic functions towards electricity production and biorenewable alcohol conversion. The molecular oxygen reduction reaction (ORR) is a long-standing scientific issue for fuel cells due to its sluggish kinetics and the poor catalyst durability. The activity and durability of an electro-catalyst is strongly related with its composition and structure. Based on this point, Pt-Fe NWs with a diameter of 2 - 3 nm were accurately prepared. They have demonstrated a high durability in sulfuric acid due to its 1-D structure, as well as a high ORR activity attributed to its tuned electronic structure. By substituting Pt with Pd using a similar synthesis route, Pd-Fe NLs were prepared and demonstrated a higher ORR activity than Pt and Pd NPs catalysts in the alkaline electrolyte. Recently, biomass-derived alcohols have attracted enormous attention as promising fuels (to replace H2) for low-temperature fuel cells. From this point of view, Pd-Ni NPs were prepared and demonstrated a high electro-catalytic activity towards ethanol oxidation. Comparing to ethanol, the biodiesel waste glycerol is more promising due to its low price and high reactivity. Glycerol (and crude glycerol) was successfully applied as the fuel in an Au-anode anion-exchange membrane fuel cell (AEMFC). By replacing Au with a more active Pt catalyst, simultaneous generation of both high power-density electricity and value-added chemicals (glycerate, tartronate, and mesoxalate) from glycerol was achieved in an AEMFC. To investigate the production of valuable chemicals from glycerol electro-oxidation, two anion-exchange membrane electro-catalytic reactors were designed. The research shows that the electro-oxidation product distribution is strongly dependent on the anode applied potential. Reaction pathways for the electro-oxidation of glycerol on Au/C catalyst have been elucidated: continuous oxidation of OH groups (to produce tartronate and mesoxalate) is predominant at lower potentials, while C-C cleavage (to produce glycolate) is the dominant reaction path at higher potentials.

Mehrwertdienst im Lebenszyklus von Sachanlagen in der Logistik

Unter dem General-Thema „Hybride Wertschöpfungsketten“ sind Zukunftsaufgaben subsummiert, die eine maßgebliche Verbesserung der Kooperationsprozesse vieler unterschiedlicher Dienste aus einem Leistungsobjekt verfolgen. Wenn das Leistungsobjekt eine Anlage ist, dann sind Wertschöpfungsketten gemeint, die von einer ersten Nutzungsspezifikation bis zur Verschrottung reichen. Mit Wertschöpfung sind sowohl Leistungen zur Herstellung und Integration dieser Anlagen in Betreiberprozesse bezeichnet, als auch diejenigen, die einen Beitrag dieser Anlage zur Wertschöpfung beim Nutzer leisten. Mit Mehrwertdiensten sind somit alle Leistungen gemeint, die an der Anlage oder für die Anlage während ihres gesamten Anlagenlebenszyklus erbracht werden. Sie dienen zur Nutzenerhöhung beim Betreiber, dem Nutzer und dem Anlagenhersteller. Damit sind Mehrwertdienste in Hybriden Wertschöpfungsketten grundsätzlich kollaborative Dienste, die üblicherweise konfliktäre Ziele mehrerer (oder sogar vieler) Interessen auflösen müssen.

Beitrag einer nutzungsabhängigen Instandhaltung zur Planung von Leistungsverfügbarkeit

Stets darauf bedacht, die Anlagen- und Maschinenverfügbarkeit bei möglichst geringem Ressourceneinsatz zu gewährleisten, wird die Rolle der Instandhaltung als unternehmerischer Wertschöpfungsfaktor immer bedeutsamer. Voraussetzung für eine Nutzbarmachung bestehender Potentiale sind neue Werkzeuge und Ansätze, deren Umsetzung eine effiziente Sicherstellung von Verfügbarkeit ermöglicht. Vor diesem Hintergrund wurde im Teilprojekt C3 des DFG Paketantrags 672 ein Konzept zur nutzungsabhängigen Instandhaltung entwickelt. Auf Grundlage des bestehenden Zusammenhangs von Nutzung und Abnutzung risikobehafteter Bauteile intralogistischer Systeme können damit die durch zukünftige Systemlasten hervorgerufenen Beanspruchungen antizipiert werden. Instandhaltungsmaßnahmen und technische Verfügbarkeiten werden dadurch anforderungsgerecht und ressourcen-optimal planbar.

The end of the corporate life cycle

This paper asks how takeover and failure hazards change as listed firms get older. The hypothesis is that they increase because firms gradually run out of growth opportunities. We find the opposite. Both takeover and failure hazard drop significantly with age. The decline in takeover hazard can be explained with Loderer, Stulz, and Waelchli’s (2013) “buggy whip makers” hypothesis: Because old firms are comparatively well-managed and are affected by limited agency problems, on average, they offer little value added potential to acquirers. Failure hazard drops because to learning. The results are robust to various alternative interpretations and cannot be explained by unobserved heterogeneity. While hazards decline with age, they do not go to zero. This explains why, eventually, all listed firms disappear

The end of the corporate life cycle

This paper asks how takeover and failure hazards change as listed firms get older. The hypothesis is that they increase because firms gradually run out of growth opportunities. We find the opposite. Both takeover and failure hazard drop significantly with age. The decline in takeover hazard can be explained with Loderer, Stulz, and Waelchli’s (2013) “buggy whip makers” hypothesis: Because old firms are comparatively well-managed and are affected by limited agency problems, on average, they offer little value added potential to acquirers. Failure hazard drops because to learning. The results are robust to various alternative interpretations and cannot be explained by unobserved heterogeneity. While hazards decline with age, they do not go to zero. This explains why, eventually, all listed firms disappear

The end of the corporate life cycle

This paper asks how takeover and failure hazards change as listed firms get older. The hypothesis is that they increase because firms gradually run out of growth opportunities. We find the opposite. Both takeover and failure hazard drop significantly with age. The decline in takeover hazard can be explained with Loderer, Stulz, and Waelchli’s (2013) “buggy whip makers” hypothesis: Because old firms are comparatively well-managed and are affected by limited agency problems, on average, they offer little value added potential to acquirers. Failure hazard drops because to learning. The results are robust to various alternative interpretations and cannot be explained by unobserved heterogeneity. While hazards decline with age, they do not go to zero. This explains why, eventually, all listed firms disappear

Why do individuals behave differently in commons dilemmas?: The case of alpine farmers using common property pastures in Grindelwald, Switzerland

The sustainable use of common-pool resources depends on users’ behaviour with regards to appropriation and provision. Most knowledge about behaviour in such situations comes from experimental research. As experiments take place in confined environments, motivational drivers and actions in the field might differ. This paper analyses farmers’ use of common property pastures in Grindelwald, Switzerland. Binary logistic regression is applied to survey data to explore the effect of farmers’ attributes on livestock endowment, appropriation and provision behaviour. Furthermore, Q methodology is used to assess the impact of broader contextual variables on the sustainability of common property pastures. It is shown that the strongest associations exist between (a) socio-economic attributes and change in livestock endowment; (b) norms and appropriation behaviour; and (c) area and pay-off and provision behaviour. Relevant contextual variables are the economic value of the resource units, off-farm income opportunities, and the subsidy structure. We conclude that with increasing farm size farmers reduce the use and maintenance of common property. Additionally, we postulate that readiness to maintain a resource increases with appropriation activities and the net returns generated from appropriation.

Commentary on "Alternative Strategies for Identifying High-Performing Charter Schools in Texas"

In the last few years policy makers and practitioners nationally have shown much interest in identifying, recognizing, and replicating successful charter schools, many of which are showing that they can educate low-income and otherwise at-risk students remarkably well. However past efforts to identify high performing schools have been problematic. Using these systematic, rigorous value-added methods, the authors identify 44 Open Enrollment charter schools that merit a “high-performer” rating. Nearly all of those campuses identified serve a disadvantaged student population. The article also finds that most of those high performers are highly cost-effective, earning high ratings on the cost-efficiency measures. The authors argue for more widespread use of value-added modeling in the state accountability system. The approach taken to identifying high-performers is sensible and fair, but any formulaic approach to school labels comes with some limitations.

Alternative Strategies for Identifying High-Performing Charter Schools in Texas

The Obama administration's recurring policy emphasis on high-performing charter schools begs the obvious question: how do you identify a high-performing charter school? That is a crucially important policy question because any evaluation strategy that incorrectly identifies charter school performance could have negative effects on the economically and/or academically disadvantaged students who frequently attend charter schools. If low-performing schools are mislabeled and allowed to persist or encouraged to expand, then students may be harmed directly. If high-performing schools are driven from the market by misinformation, then students will lose access to programs and services that can make a difference in their lives. Most of the scholarly analysis to date has focused on comparing the performance of students in charter schools to that of similar students in traditional public schools (TPS). By design, that research measures charter school performance only in relative terms. Charter schools that outperform similarly situated, but low performing, TPSs have positive effects, even if the charter schools are mediocre in an absolute sense. This analysis describes strategies for identifying high-performing charter schools by comparing charter schools with one another. We begin by describing salient characteristics of Texas charter schools. We follow that discussion with a look at how other researchers across the country have compared charter school effectiveness with TPS effectiveness. We then present several metrics that can be used to identify high-performing charter schools. Those metrics are not mutually exclusive—one could easily justify using multiple measures to evaluate school effectiveness—but they are also not equally informative. If the goal is to measure the contributions that schools are making to student knowledge and skills, then a value-added approach like the ones highlighted in this report is clearly superior to a levels-based approach like that taken under the current accountability system.

Funciones de volumen para especies de bosque secundario de la Reserva Guaraní : Misiones (Argentina)

Se ajustaron y evaluaron funciones de volumen de fuste para un grupo de especies arbóreas de un bosque secundario. El bosque del cual se obtuvieron los datos se encuentra situado en la Reserva de Biosfera Yabotí, en la provincia de Misiones, Argentina. Se trabajó sobre una muestra de 216 árboles, correspondientes a las 14 especies presentes más importantes respecto de la estructura del bosque y/o del valor económico de las mismas. De las nueve funciones evaluadas, cinco de ellas tuvieron coeficientes de determinación ajustados superiores a 0,99. Por su destacado comportamiento estadístico global se seleccionó una expresión resultante de modificar el modelo de Naslund. Utilizando los resultados de esta función se construyó una tabla de volumen de fustes individuales en la cual el diámetro a 1,3 m de altura (D) y la altura de fuste (H) fueron las variables de entrada para árboles de un bosque secundario de aproximadamente 30 años de edad. Los D observados fueron desde 5,4 hasta 42 cm y el rango de H entre 1,4 y 16 m. Los modelos seleccionados dieron resultados satisfactorios para predecir volúmenes y cantidad de biomasa acumulada en los fustes de árboles del bosque secundario analizado en este trabajo.

Los cambios en el proceso de producción del algodón en el Chaco en las últimas décadas y sus consecuencias en las condiciones de vida de minifundistas y trabajadores vinculados

En el artículo nos planteamos los cambios que desde los años 1990 ha sufrido la producción de algodón en la Provincia del Chaco -principal referente nacional del cultivo- y cómo estos fueron modificando la estructura de vida de los agentes históricamente vinculados, en especial, los trabajadores y los minifundistas hoy prácticamente excluidos de dicho proceso. Entre los numerosos cambios, los más relevantes son los vinculados al proceso de tecnificación, a la desarticulación en el territorio de cadenas de valor agregado y a la diversificación hacia otros cultivos como las oleaginosas y, notoriamente, al avance del cultivo de soja sobre hectáreas antes destinadas al algodón. Como consecuencia de dichos procesos de cambio, se evidencia la imposibilidad -por parte de los minifundistas- de sostener una producción rentable, la pérdida de numerosas fuentes de trabajo directas e indirectas, el aumento de la pobreza, la emigración hacia los cordones periféricos urbanos (Gran Resistencia, Gran Rosario) y el deterioro de las condiciones laborales de quienes aún permanecen dentro del sistema productivo algodonero. Las políticas públicas, tanto locales como nacionales, también son un punto de interés en el análisis puesto que tienen gran repercusión en el actual estado de la situación

Dinámicas del sector agropecuario argentino en el siglo XXI : La distribución del ingreso en regiones pampeanas y extrapampeanas

En este trabajo se analizan una serie de aspectos que resultan centrales para comprender la situación de los trabajadores en el sector agropecuario. En primer lugar, se contrapone la evolución del producto del sector con su capacidad para generar puestos de trabajo. Luego, se da cuenta de las condiciones de empleo poniendo especial énfasis en el estudio del grado de informalidad y de los niveles salariales. Se compara, a continuación, la distribución primaria del ingreso del sector con la de la economía nacional en su conjunto. Este análisis distributivo se complementa con dos estudios de caso que intentan poner de manifiesto las implicancias de los distintos cultivos llevados a cabo en diferentes regiones. El estudio muestra que el salario medio del sector agropecuario sigue estando muy por debajo de la remuneración promedio de la economía y que, además, la participación de los salarios en el valor agregado del sector se ha reducido desde la salida de la Convertibilidad, incluso en un contexto de aumento del salario medio sectorial. Finalmente, sobre la base del análisis de los casos mencionados, se asocia la distribución del ingreso con los distintos cultivos y las regiones donde estos se desarrollan. Al respecto, se discute el rol de las ganancias individuales como guía orientadora del uso de la tierra cultivable

Los cambios en el proceso de producción del algodón en el Chaco en las últimas décadas y sus consecuencias en las condiciones de vida de minifundistas y trabajadores vinculados

En el artículo nos planteamos los cambios que desde los años 1990 ha sufrido la producción de algodón en la Provincia del Chaco -principal referente nacional del cultivo- y cómo estos fueron modificando la estructura de vida de los agentes históricamente vinculados, en especial, los trabajadores y los minifundistas hoy prácticamente excluidos de dicho proceso. Entre los numerosos cambios, los más relevantes son los vinculados al proceso de tecnificación, a la desarticulación en el territorio de cadenas de valor agregado y a la diversificación hacia otros cultivos como las oleaginosas y, notoriamente, al avance del cultivo de soja sobre hectáreas antes destinadas al algodón. Como consecuencia de dichos procesos de cambio, se evidencia la imposibilidad -por parte de los minifundistas- de sostener una producción rentable, la pérdida de numerosas fuentes de trabajo directas e indirectas, el aumento de la pobreza, la emigración hacia los cordones periféricos urbanos (Gran Resistencia, Gran Rosario) y el deterioro de las condiciones laborales de quienes aún permanecen dentro del sistema productivo algodonero. Las políticas públicas, tanto locales como nacionales, también son un punto de interés en el análisis puesto que tienen gran repercusión en el actual estado de la situación

Dinámicas del sector agropecuario argentino en el siglo XXI : La distribución del ingreso en regiones pampeanas y extrapampeanas

En este trabajo se analizan una serie de aspectos que resultan centrales para comprender la situación de los trabajadores en el sector agropecuario. En primer lugar, se contrapone la evolución del producto del sector con su capacidad para generar puestos de trabajo. Luego, se da cuenta de las condiciones de empleo poniendo especial énfasis en el estudio del grado de informalidad y de los niveles salariales. Se compara, a continuación, la distribución primaria del ingreso del sector con la de la economía nacional en su conjunto. Este análisis distributivo se complementa con dos estudios de caso que intentan poner de manifiesto las implicancias de los distintos cultivos llevados a cabo en diferentes regiones. El estudio muestra que el salario medio del sector agropecuario sigue estando muy por debajo de la remuneración promedio de la economía y que, además, la participación de los salarios en el valor agregado del sector se ha reducido desde la salida de la Convertibilidad, incluso en un contexto de aumento del salario medio sectorial. Finalmente, sobre la base del análisis de los casos mencionados, se asocia la distribución del ingreso con los distintos cultivos y las regiones donde estos se desarrollan. Al respecto, se discute el rol de las ganancias individuales como guía orientadora del uso de la tierra cultivable