Base-free, one-pot chemocatalytic conversion of glycerol to methyl lactate using supported gold catalysts

We report an efficient one-pot conversion of glycerol (GLY) to methyl lactate (MLACT) in methanol in good yields (73 % at 95 % GLY conversion) by using Au nanoparticles on commercially available ultra-stable zeolite-Y (USY) as the catalyst (160 °C, air, 47 bar pressure, 0.25 M GLY, GLY-to-Au mol ratio of 1407, 10 h). The best results were obtained with zeolite USY-600, a catalyst that has both Lewis and Brønsted sites. This methodology provides a direct chemo-catalytic route for the synthesis of MLACT from GLY. MLACT is stable under the reaction conditions, and the Au/USY catalyst was recycled without a decrease in the activity and selectivity. From glycerol to green building blocks and solvents! An efficient, base-free conversion of glycerol to methyl lactate in methanol is reported, achieving good yields (73 % at 95 % glycerol conversion) using Au/ultra-stable zeolite-Y (USY) as the catalyst and environmentally benign oxygen as the oxidant by combining two separate reaction steps efficiently in a one pot procedure. The Au/USY catalyst can be recycled without a decrease in the activity and selectivity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hot-spots during the calcination of MCM-41:a SAXS comparative analysis of a soft mesophase

The phenomenon of microscopic hot-spots, during the calcination of MCM-41, was investigated by quantifying the magnitude of the temperature increase during the calcination of a soft MCM-41 mesophase using a SAXS comparative study. This was performed by thermally treating a soft material that was detemplated via Fenton chemistry followed by equilibrating and drying in a low-surface-tension solvent (n-butanol or N,N-dimethylformamide); these samples have limited structural shrinkage. The resulting samples were thermally treated at increasing temperatures, and the structural shrinkage was compared with that of the directly calcined material. By comparing the structural shrinkage, it was found that the microscopic temperature increase would fall between 190 and 250 C, as deduced from N,N-dimethyl-formamide and n-butanol. The order of magnitude of the temperature increase appears to be consistent with the well-known glow effect. It is, however, substantially higher than the experimentally determined macroscopic temperature increase. Several aspects are discussed to interpret this difference. © 2013 Elsevier B.V.

Detemplation of soft mesoporous silica nanoparticles with structural preservation

A mild protocol that allows the template removal of soft un-aged silica nanoparticles was investigated. After oxidizing the organic template by Fenton chemistry, a good structural preservation is only achieved when the material is equilibrated and dried in a low-surface tension solvent. This avoids excessive capillary stress induced by the high surface tension of water, a major component in the Fenton reaction medium. The Fenton reaction should be carried out under mild conditions as well; otherwise the sample deteriorates by extensive hydrolysis, and capillary stress, and the structural ordering diminishes severely. We propose employing 10 ppm Fe concentration at 70 °C for 24 h for the cetyltrimethylammonium bromide template. The proposed protocol involves 2 steps resulting in an overall significantly higher pore volume attributed to the wider pores and limited particle agglomeration, while the calcined counterpart evidences aggregation and loss of the hexagonal ordering. n-BuOH exchange is unnecessary when the mesophase is stabilized by ageing, as the structure resists the water capillary stress. © The Royal Society of Chemistry 2013.

Direct activation of microcrystalline zeolites

In this work a direct activation route of zeolites is assessed. It consists of NH4-exchanging the as-synthesized solids before removing the organic template. Calcination afterwards serves to combust the organic template and creates the Brønsted sites directly; thus applying merely a single thermal step. This method simplifies their activation and the material suffers less thermal stress. The approach was particularly effective for microcrystalline beta and ferrierite zeolites. Thorough investigation of the template content and materials' texture points out to three relevant effects that can explain the effective exchange process: partial removal of the template during exchange creates substantial microporosity (ferrierite), the remaining template is reorganized within the pores (ferrierite) and finally, void space can exist due to the non-perfect matching between the network and template (beta). This shorter method appears suited for microcrystalline zeolites; it was ineffective for crystalline MFI types. © 2013 Elsevier B.V. All rights reserved.

Condensation-enhanced self-assembly as a route to high surface area α-aluminas

High surface area nanosized α-alumina has been obtained by thermally treating a sol-gel-derived mesophase at 1200 C; the mesophase was synthesized by a sol-gel route involving evaporation induced self-assembly (EISA) of a hydrolyzed gel from Al-tri-sec-butoxide in s-BuOH in the presence of a nonionic surfactant (EO20PO70EO20), HCl as catalyst, and water (H2O/Al = 6). The activated material renders moderate surface areas of about 8.4-10 m2 g-1, associated with significant crystallite coarsening. The key aspect to produce smaller crystallites is making the mesophase more resistant to coarsening. This was achieved by enhancing the condensation step by treating the hydrolyzed gel with tetrabutyl ammonium hydroxide (TBAOH) before evaporation. The characteristics of the mesophase indicate condensation of the primary particles with less AlO5 unsaturated sites, at the expense of a lower solid yield due to small crystallites dissolution. The activated TBAOH condensed EISA material is composed of α-alumina aggregated crystallites of about 60-100 nm, and the material possesses surface areas ranging from 16 to 24 m2 g -1 due to the improved resistance to coarsening. At least two aspects are suggested to play a role in this. The worm-hole morphology of the mesophase aggregates yields high particle coordination, which favors densification rather than coarsening. Furthermore, the decrease of the AlO5 defect sites by the TBAOH condensation makes the mesophase less reactive and consequently more resistant to coarsening. © 2013 American Chemical Society.

Thermal detemplation of SBA-15 mesophases. Effect of the activation protocol on the framework contraction

The potential use of the solvothermal extraction (SE) as a preliminary step to calcination for detemplating SBA-15 mesophases is investigated; aiming to reduce the amount of organics to be burnt and thereby the corresponding structural shrinkage. A systematic study was carried out by soxhlet extraction on mesophases hydrothermally aged between 90 and 130 C. The mesophases containing variable amounts of template were then treated by calcination or pyrolysis/calcination. TGA was applied to quantify the template amount after the various treatments. The as obtained materials were characterized by SAXS and Ar ad/desorption for structural and textural information while 1H NMR gave information about the integrity of the as-recycled template. The study shows that solvothermal conditions remove considerably the template, typically from 50 to 10-20 wt.%, mainly extracted from the primary mesopores. Possible reuse of the extracted template is questionable as it is poor in polyethyleneoxide compared to the synthesis block-copolymer, Pluronic P123. For all thermal protocols applied (direct calcination, calcination after solvent-extraction or pyrolysis/calcination after solvent extraction), the thermal shrinkage decreases with the aging temperature; that is consistent with the condensation degree of the silica. For each mesophase, it was found that the thermal shrinkage becomes less pronounced when the material is fully templated; thus the template can serve as structural support or can control the mass transfer of O2 and thereby the oxidation rate of the template burning. © 2013 Elsevier Inc. All rights reserved.

Oxidative dehydrogenation of ethylbenzene to styrene over alumina:effect of calcination

Commercially available γ-Al2O3 was calcined at temperatures between 500 and 1200 °C and tested for its performance in the oxidative ethylbenzene dehydrogenation (ODH) over a wide range of industrially-relevant conditions. The original γ-Al2O 3, as well as η- and α-Al2O3, were tested. A calcination temperature around 1000/1050 °C turned out to be optimal for the ODH performance. Upon calcination the number of acid sites (from 637 to 436 μmol g-1) and surface area (from 272 to 119 m 2 g-1) decrease, whereas the acid site density increases (from 1.4 to 2.4 sites per nm2). Less coke, being the active catalyst, is formed during ODH on the Al-1000 sample compared to γ-Al 2O3 (30.8 wt% vs. 21.6 wt%), but the coke surface coverage increases. Compared with γ-Al2O3, the EB conversion increased from 36% to 42% and the ST selectivity increased from 83% to 87%. For an optimal ST selectivity the catalyst should contain enough coke to attain full conversion of the limiting reactant oxygen. The reactivity of the coke is changed due to the higher density and strength of the Lewis acid sites that are formed by the high temperature calcination. The Al-1000 sample and all other investigated catalysts lost ODH activity with time on stream. The loss of selectivity towards more COX formation is directly correlated with the amount of coke. © The Royal Society of Chemistry 2013.

Catalyst studies on the ring opening of tetrahydrofuran-dimethanol to 1,2,6-hexanetriol

The metal catalyzed hydrogenolysis of the biomass-derived THF-dimethanol to 1,2,6-hexanetriol using heterogeneous catalysts was investigated. Bimetallic Rh-Re catalysts (4 wt% Rh and a Re/Rh (mol. ratio of 0.5) on a silica support gave the best performance and 1,2,6-hexanetriol was obtained in 84% selectivity at 31% conversion (120 C, 80 bar, 4 h); the selectivity reaches a maximum of 92% at 80 C. The product distribution at prolonged reaction times or higher temperatures or both shows the formation of diols and mono-alcohols, indicating that the 1,2,6-hexanetriol is prone to subsequent hydrodeoxygenation reactions. Different silica supports were investigated and optimal results were obtained with an amorphous silica featuring an intermediate surface area and an average mesopore size of about 6 nm. TPR and XPS surface analysis support the presence of mixed Rh and Re particles. The redox Reδ+/ReTotal surface ratio correlates with the conversion in a volcano type dependency. Both gas phase as well as Rh200Re1OH cluster DFT calculations support an acid-metal bifunctional mechanism and explain the products distribution. © 2013 Elsevier B.V. All rights reserved.

Stabilization of self-assembled alumina mesophases

An efficient route to stabilize alumina mesophases derived from evaporation-induced self-assembly is reported after investigating various aspects in-depth: influence of the solvent (EtOH, s-BuOH, and t-BuOH) on the textural and structural properties of the mesophases based on aluminum tri-sec-butoxide (ATSB), synthesis reproducibility, role of nonvolatile acids, and the crystallization and thermal stability of the crystalline counterparts. Mesophase specific surface area and pore uniformity depend notably on the solvent; s-BuOH yields the highest surface area and pore uniformity. The optimal mesophase synthesis is reproducible with standard deviations in the textural parameters below 5%. The most pore-uniform mesophases from the three solvents were thermally activated at 1023 K to crystallize them into γ-alumina. The s-BuOH mesophase is remarkably thermally stable, retaining the mesoscopic wormhole order with 300 m2/g (0.45 cm3/g) and an increased acidic site density. These features are not obtained with EtOH or t-BuOH, where agglomerated γ-Al2O3 crystallites are formed with lower surface areas and broader pore size distributions. This was rationalized by the increase of the hydrolysis rate using EtOH and t-BuOH. t-BuOH dehydrates under the synthesis conditions or reacts with HCl, situations that increase the water concentration and rate of hydrolysis. It was found that EtOH exchanges rapidly, producing a highly reactive Al-ethoxide, thus enhancing the hydrolysis rate as well. Particle heterogeneity with random packing of fibrous and wormhole morphologies, attributed to the high hydrolysis rate, was observed for mesophases derived from both solvents. Such a low particle coordination favors coarsening with enlargement of the pore size distribution upon thermal treatment, explaining the lower thermal stability. Controlled hydrolysis and formation of low-polymerized Al species in s-BuOH are possibly responsible for the adequate assembly onto the surfactant. This was verified by the formation of a regular distribution of relatively size-uniform nanoparticles in the mesophase; high particle coordination prevents coarsening, favors densification, and maintains a relatively uniform pore size distribution upon thermal treatment. The acid removal in the evaporation is another key factor to promote network condensation in this route. © 2013 American Chemical Society.

Entre el terror y la irrealidad: La narrativa poetica postmoderna de Reinaldo Arenas

This study focuses on the works of Cuban writer Reinaldo Arenas, one of the most prolific and controversial Latin American authors in the second half of the twentieth century. First, I propose Arenas as the creator of the Cuban revolutionary novel (a term coined by critics when referring to the narrative written after the revolution), within the scope of postmodern historiographic metafiction and against the trend of the official revolutionary novel promoted by the political establishment. Through the analysis of the five novels of the pentagony and other texts, my study follows the tragic journey of the antihero protagonist, from adolescence into adulthood, registering the correlation between his existential crisis and the narrative historical discourse. Contemporary Cuba from 1959 onwards—the historical-political circumstances that afflicted and overwhelmed him the most—becomes the point of reference to deconstruct reality and reaffirm the existence of a “self” threatened by the violence of a totalitarian discourse. Out of the fragments of this reality, Arenas undertook a radical reconstruction in which he inverted and questioned every inherited cultural value, as well as the power structures. Within this context, Arenas projects what I call “the Cuban hideous unreal”, an ontological and literary vision antagonistic to the carpentirean concept of the American “marvelous real”. ^ Despite the ostracism Reinaldo Arenas suffered for ten years, this study shows how he established through his work a meditative dialogue with himself and the common man. This perspective formulates a permanent literary and philosophic reflection with thinkers and writers of his country and the West, as the basis for a rejection of the Cuban reality. The resultant interdisciplinary and postmodern dialogue constitutes one of the most significant and distinctive contributions of his work. ^

Carmen de Burgos: La educacion de la mujer y la literatura de viajes como genero narrativo

This study analyzes Carmen de Burgos' European travel literature, and focuses on two themes: education and travel literature as a literary genre. An examination of her travel literature reveals two essential elements related to her view of education. The first is the influence that the European educational system had on her way of thinking, particularly with respect to the idea of tolerance, the practice of hygiene, and the important role of nature in education. The second is the development of her view of education as the foundation for the emancipation of women in Spain. Carmen de Burgos espoused the view that the reform of the Spanish educational system was the primary and foundational goal to further social, political and economic progress of women in Spain at the end of the 19th and beginning of the 20th Century. ^ In the second part of this dissertation I support the theory that her travel literature was her main source to convey to Spanish women the need for social change. I do this by analyzing four properties that are considered characteristic of women's travel literature: (1) the woman as a hero, (2) scientific authority of women, (3) feminine style, and (4) feminine content. I argue that Carmen de Burgos's travel literature uses these properties to facilitate her access to women audiences and to assure that this audience regarded her as an authoritative voice. ^

Autonomic and embedded wireless sensor protocols for critical infrastructures

The tragic events of September 11th ushered a new era of unprecedented challenges. Our nation has to be protected from the alarming threats of adversaries. These threats exploit the nation's critical infrastructures affecting all sectors of the economy. There is the need for pervasive monitoring and decentralized control of the nation's critical infrastructures. The communications needs of monitoring and control of critical infrastructures was traditionally catered for by wired communication systems. These technologies ensured high reliability and bandwidth but are however very expensive, inflexible and do not support mobility and pervasive monitoring. The communication protocols are Ethernet-based that used contention access protocols which results in high unsuccessful transmission and delay. An emerging class of wireless networks, named embedded wireless sensor and actuator networks has potential benefits for real-time monitoring and control of critical infrastructures. The use of embedded wireless networks for monitoring and control of critical infrastructures requires secure, reliable and timely exchange of information among controllers, distributed sensors and actuators. The exchange of information is over shared wireless media. However, wireless media is highly unpredictable due to path loss, shadow fading and ambient noise. Monitoring and control applications have stringent requirements on reliability, delay and security. The primary issue addressed in this dissertation is the impact of wireless media in harsh industrial environment on the reliable and timely delivery of critical data. In the first part of the dissertation, a combined networking and information theoretic approach was adopted to determine the transmit power required to maintain a minimum wireless channel capacity for reliable data transmission. The second part described a channel-aware scheduling scheme that ensured efficient utilization of the wireless link and guaranteed delay. Various analytical evaluations and simulations are used to evaluate and validate the feasibility of the methodologies and demonstrate that the protocols achieved reliable and real-time data delivery in wireless industrial networks.

Post-revolutionary post-modernism: Central American detective fiction by the turn of the 21st century

Contemporary Central American fiction has become a vital project of revision of the tragic events and the social conditions in the recent history of the countries from which they emerge. The literary projects of Sergio Ramirez (Nicaragua), Dante Liano (Guatemala), Horacio Castellanos Moya (El Salvador), and Ramon Fonseca Mora (Panama), are representative of the latest trends in Central American narrative. These trends conform to a new literary paradigm that consists of an amalgam of styles and discourses, which combine the testimonial, the historical, and the political with the mystery and suspense of noir thrillers. Contemporary Central American noir narrative depicts the persistent war against social injustice, violence, criminal activities, as well as the new technological advances and economic challenges of the post-war neo-liberal order that still prevails throughout the region. ^ Drawing on postmodernism theory proposed by Ihab Hassan, Linda Hutcheon and Brian MacHale, I argued that the new Central American literary paradigm exemplified by Sergio Ramirez's El cielo llora por mí, Dante Liano's El hombre de Montserrat, Horacio Castellanos Moya's El arma en el hombre and La diabla en el espejo , and Ramon Fonseca Mora's El desenterrador, are highly structured novels that display the characteristic marks of postmodern cultural expression through their ambivalence, which results from the coexistence of multiple styles and conflicting ideologies and narrative trends. The novels analyzed in this dissertation make use of a noir sensitivity in which corruption, decay and disillusionment are at their core to portray the events that shaped the modern history of the countries from which they emerge. The revolutionary armed struggle, the state of terror imposed by military regimes and the fight against drug trafficking and organized crime, are among the major themes of these contemporary works of fiction, which I have categorized as perfect examples of the post-revolutionary post-modernism Central American detective fiction at the turn of the 21st century.^

The Fullness of time

THE FULLNESS OF TIME is a novel about the quest for identity that transcends the limitations of moral duty, social status, and cultural conventions. Set in Tarpon Springs, Florida, in 1969, it is the story of Victor Lucas, a young Greek immigrant forced to go to war in Vietnam in another man's place in order to save the woman he loves. He must survive the war to return and reclaim his love and his rightful place in society. Based on the archetypal hero's quest as articulated by Joseph Campbell, the narrative is told from the limited third-person perspective of the main character. Though the journey is particular to Tarpon Springs in the 1960s, it echoes the human struggle and triumph in the wanderings of Ulysses. The novel's influences include Thomas Hardy's The Mayor of Casterbridge, but is also thematically related to contemporary works exploring cultural turbulence and upheaval.

This was uncalled for : Dave Eggers' A heartbreaking work of staggering genius subverts the genre of traditional autobiography as an attempt at rendering his life

The purpose of this thesis was to explore why and how the author Dave Eggers subverts the genre of traditional autobiography in his memoir A Heartbreaking Work of Staggering Genius. I compared Eggers' work to Gertrude Stein's The Autobiography of Alice B. Toklas and William S. Burroughs' Junky. I found that like Stein and Burroughs, Eggers utilized various rhetorical devices outside of traditional autobiography because he could not find the means to express himself within the genre. Eggers employed various rhetorical methods reserved for fictional texts, such as stream of consciousness, characterization, and irony, in order to reconcile his feelings towards his parents' deaths and render those feelings in his memoir. I established that Eggers concluded his memoir with impossibility of arriving at one Meaning that could summate his tragic experience. Thus, I proved that Eggers gave the reader the only authentic interpretation he could: the memoir as a small, incomplete glimpse into his life.