Designer catalysts for biodiesel synthesis

The combination of dwindling oil reserves and growing concerns over carbon dioxide emissions and associated climate change is driving the urgent development of clean, sustainable energy supplies. Biodiesel is a non-toxic and biodegradable fuel, with the potential for closed CO2 cycles and thus vastly reduced carbon footprints compared with petroleum. However, current manufacturing routes employing soluble catalysts are very energy inefficient, with their removal necessitating an energy intensive separation to purify biodiesel, which in turn produces copious amounts of contaminated aqueous waste. The introduction of non-food based feedstocks and technical advances in heterogeneous catalyst and reactor design are required to ensure that biodiesel remains a key player in the renewable energy sector for the 21st century. Here we report on the development of tuneable solid acid and bases for biodiesel synthesis, which offer several process advantages by eliminating the quenching step and allowing operation in a continuous reactor. Significant progress has been made towards developing tuneable solid base catalysts for biodiesel synthesis, including Li/CaO [1], Mg-Al hydrotalcites [2] and calcined dolomite [3] which exhibit excellent activity for triglyceride transesterification. However, the effects of solid base strength on catalytic activity in biodiesel synthesis remains poorly understood, hampering material optimisation and commercial exploitation. To improve our understanding of factors influencing solid base catalysts for biodiesel synthesis, we have applied a simple spectroscopic method for the quantitative determination of surface basicity which is independent of adsorption probes. Such measurements reveal how the morphology and basicity of MgO nanocrystals correlate with their biodiesel synthesis activity [4]. While diverse solid acids and bases have been investigated for TAG transesterification, the micro and mesoporous nature of catalyst systems investigated to date are not optimal for the diffusion of bulky and viscous C16-C18 TAGs typical of plant oils. The final part of this presentation will address the benefits of designing porous networks comprising interconnected hierarchical macroporous and mesoporous channels (Figure 1) to enhance mass-transport properties of viscous plant oils during biodiesel synthesis [5]. References: [1] R.S. Watkins, A.F. Lee, K. Wilson, Green Chem., 2004, 6, 335. [2]D.G. Cantrell, L.J. Gillie, A.F. Lee and K. Wilson, Appl. Catal. A, 2005, 287,183. [3] C. Hardacre, A.F. Lee, J.M. Montero, L. Shellard, K.Wilson, Green Chem., 2008, 10, 654. [4] J.M. Montero, P.L. Gai, K. Wilson, A.F. Lee, Green Chem., 2009, 11, 265. [5] J. Dhainaut, J.-P. Dacquin, A.F. Lee, K. Wilson, Green Chem., 2010, 12, 296.

Glutaredoxin-1 up-regulation induces soluble vascular endothelial growth factor receptor 1, attenuating post-ischemia limb revascularization

Glutaredoxin-1 (Glrx) is a cytosolic enzyme that regulates diverse cellular function by removal of GSH adducts from S-glutathionylated proteins including signaling molecules and transcription factors. Glrx is up-regulated during inflammation and diabetes. Glrx overexpression inhibits VEGF-induced endothelial cell (EC) migration. The aim was to investigate the role of up-regulated Glrx in EC angiogenic capacities and in vivo revascularization in the setting of hind limb ischemia. Glrx overexpressing EC from Glrx transgenic mice (TG) showed impaired migration and network formation and secreted higher level of soluble VEGF receptor 1 (sFlt), an antagonizing factor to VEGF. After hind limb ischemia surgery Glrx TG mice demonstrated impaired blood flow recovery, associated with lower capillary density and poorer limb motor function compared to wild type littermates. There were also higher levels of anti-angiogenic sFlt expression in the muscle and plasma of Glrx TG mice after surgery. Non-canonical Wnt5a is known to induce sFlt. Wnt5a was highly expressed in ischemic muscles and EC from Glrx TG mice, and exogenous Wnt5a induced sFlt expression and inhibited network formation in human microvascular EC. Adenoviral Glrx-induced sFlt in EC was inhibited by a competitive Wnt5a inhibitor. Furthermore, Glrx overexpression removed GSH adducts on p65 in ischemic muscle and EC, and enhanced nuclear factor kappa B (NF-kB) activity which was responsible for Wnt5a-sFlt induction. Taken together, up-regulated Glrx induces sFlt in EC via NF-kB -dependent Wnt5a, resulting in attenuated revascularization in hind limb ischemia. The Glrx-induced sFlt may be a part of mechanism of redox regulated VEGF signaling.

Adjusting WSMO API Reference Implementation to Support More Reliable Entity Persistence

* The research has been partially supported by INFRAWEBS - IST FP62003/IST/2.3.2.3 Research Project No. 511723 and “Technologies of the Information Society for Knowledge Processing and Management” - IIT-BAS Research Project No. 010061.

Solid base catalysed 5-HMF oxidation to 2,5-FDCA over Au/hydrotalcites:fact or fiction?

Nanoparticulate gold has emerged as a promising catalyst for diverse mild and efficient selective aerobic oxidations. However, the mechanism of such atom-economical transformations, and synergy with functional supports, remains poorly understood. Alkali-free Mg-Al hydrotalcites are excellent solid base catalysts for the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furan dicarboxylic acid (FDCA), but only in concert with high concentrations of metallic gold nanoparticles. In the absence of soluble base, competitive adsorption between strongly-bound HMF and reactively-formed oxidation intermediates site-blocks gold. Aqueous NaOH dramatically promotes solution phase HMF activation, liberating free gold sites able to activate the alcohol function within the metastable 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) reactive intermediate. Synergistic effects between moderate strength base sites within alkali-free hydrotalcites and high gold surface concentrations can afford highly selective and entirely heterogeneous catalysts for aqueous phase aldehyde and alcohol cascade oxidations pertinent to biomass transformation.

Serum procalcitonin, interleukin-6, soluble intercellular adhesin molecule-1 and IgG to short-chain exocellular lipoteichoic acid as predictors of infection in total joint prosthesis revision

The diagnosis of prosthetic joint infection and its differentiation from aseptic loosening remains problematic. The definitive laboratory diagnostic test is the recovery of identical infectious agents from multiple intraoperative tissue samples; however, interpretation of positive cultures is often complex as infection is frequently associated with low numbers of commensal microorganisms, in particular the coagulase-negative staphylococci (CNS). In this investigation, the value of serum procalcitonin (PCT), interleukin-6 (IL-6) and soluble intercellular adhesion molecule-1 (sICAM-1) as predictors of infection in revision hip replacement surgery is assessed. Furthermore, the diagnostic value of serum IgG to short-chain exocellular lipoteichoic acid (sce-LTA) is assessed in patients with infection due to CNS. Presurgical levels of conventional serum markers of infection including C-reactive protein (CRP), erythrocyte sedimentation rate (ESR) and white blood cell count (WBC) is also established. Forty-six patients undergoing revision hip surgery were recruited with a presumptive clinical diagnosis of either septic (16 patients) or aseptic loosening (30 patients). The diagnosis was confirmed microbiologically and levels of serum markers were determined. Serum levels of IL-6 and sICAM-1 were significantly raised in patients with septic loosening (P=0.001 and P=0.0002, respectively). Serum IgG to sce-LTA was elevated in three out of four patients with infection due to CNS. In contrast, PCT was not found to be of value in differentiating septic and aseptic loosening. Furthermore, CRP, ESR and WBC were significantly higher (P=0.0001, P=0.0001 and P=0.003, respectively) in patients with septic loosening. Serum levels of IL-6, sICAM-1 and IgG to sce-LTA may provide additional information to facilitate the diagnosis of prosthetic joint infection.

Phosphorus enrichment effects on interactions among the ecosystem components in a long-hydroperiod oligotrophic marsh in Everglades National Park

Hydrology and a history of oligotrophy unite the massive landscape comprising freshwater marsh in Everglades National Park. With restoration of water flow to the Everglades, phosphorus (P) enrichment, both from agricultural and domestic sources, may increase nutrient load to the marsh ecosystem. Previous research of P enrichment of Everglades soil, periphyton, and macrophytes revealed each of these ecosystem components responds to increased P loads with increased production and nutrient content. Interactions among these ecosystem components and how P affects the magnitude and direction of interaction are poorly understood and are the focus of my research. Here I present results of a two-year, two-factor experiment of P enrichment and manipulation in Everglades National Park. I quantified biomass, nutrient content, and production for periphyton and macrophyes and found macrophyte removal drives change in nutrient content, biomass, and production of periphyton. Periphyton removal did not appear to control macrophyte dynamics. Soil chemical and physical characteristics were explained primarily by site differences but there was an enrichment effect of soil porewater nitrite + nitrate, nitrite, and soluble reactive phosphorus. Flocculent materials production and depth were significantly affected by macrophyte removal where depth and production were significantly greater with the no macrophyte treatment. The dominant macrophyte of the marsh, Eleocharis cellulosa, increased more in the unenriched marsh than in the enriched marsh. The combination of these findings suggests that dynamics in floc and periphyton are controlled primarily by the presence of periphyton and that this relationship is significantly affected by low-level P enrichment. These results may be valuable in their application to both managers and policy makers who are involved in the Everglades restoration process. ^

Environmental analysis of polar herbicides in complex organic-rich matrices by high performance liquid chromatography atmospheric pressure ionization mass spectrometry (HPLC-API-MS)

A comprehensive forensic investigation of sensitive ecosystems in the Everglades Area is presented. Assessing the background levels of contamination in these ecosystems represents a vital resource to build up forensic evidence required to enforce future environmental crimes within the studied areas. This investigation presents the development and validation of a fractionation and isolation method for two families of herbicides commonly applied in the vicinity of the study area, including phenoxy acids like 2,4-D, MCPA, and silvex; as well as the most common triazine-based herbicides like atrazine, prometyne, simazine and related metabolites like DIA and DEA. Accelerated solvent extraction (ASE) and solid phase extraction (SPE) were used to isolate the analytes from abiotic matrices containing large amounts of organic material. Atmospheric-pressure ionization (API) with electrospray ionization in negative mode (ESP-), and Chemical Ionization in the positive mode (APCI+) were used to perform the characterization of the herbicides of interest.

(Table 2, Page 106-107) Composition of the HCl-soluble fraction in Barents Sea iron-manganese deposits

Ferromanganese concretions from ten stations in the Barents Sea have been analysed for 24 elements. The deposits occur as discoidal and flat concretions and as coatings, in the latter case on lithified or detrital material or as extensive pavements on the Svalbard shelf. The concretions are compositionally similar to Baltic concretions but differ considerably from deep-ocean nodules, particularly in Cu, Ni and Co contents. Statistical analyses reveal distinct correlations between Mn, Na, Ba, Ni and Cu; the Mn-rich coatings showed enrichment of Mo, Zn and possibly Co in a Mn-phase. The iron phase holds high concretions of P and As. Two iron-rich concretions with high contents of P, Ca, Sr, Y, Yb and La were found east and northeast of Spitsbergen Banken, probably indicating upwelling of nutrient-rich, cold polar water along the Svalbard shelf.

(Table 3) Sulfur and oxygen isotopic composition of cold water soluble sulfate, and strontium content and isotopic composition of upper Miocene evaporite samples recovered from DSDP Site 23-227

The origin of three Red Sea submarine brine pools was investigated by analysis of the S and O isotope ratios of dissolved sulfate and Sr isotope ratios of dissolved Sr in the brines. Sulfur and O isotope ratios of sulfate and Sr isotope ratios of evaporitic source rocks for the brines were measured for comparison. The S, O and Sr isotope ratios of evaporites recovered from DSDP site 227 are consistent with an upper Miocene evaporites age. The Valdivia Deep brine formed by karstic dissolution of Miocene evaporites by overlying seawater and shows no signs of hydrothermal input. The Suakin Deep brines are derived from, or have isotopically exchanged with Miocene or older evaporites. There has been only minor dilution of the brine by overlying seawater. Strontium isotope ratios of Suakin brine may indicate addition of a minor (15%) amount of volcanic Sr to the brine, but there is no evidence of high temperature brine-rock interaction. The sulfate in the Atlantis II brine was apparently derived from seawater. The O isotope ratio of sulfate in the present Atlantis II brine could reflect isotopic exchange between seawater sulfate and the brine at approximately 255°C. Approximately 30% of the Sr in the Atlantis II brine is derived from the underlying basalt, probably by hydrothermal leaching. Atlantis II brine is the only known example from the Red Sea which has a significant high-temperature hydrothermal history.

(Table 5, page 626), Tin and main metal elements composition of ferromanganese concretions (acid-soluble fractions)

Concentrations of tin in sea water decreased from estuarine and shelf (0.02-0.04 µg/kg) to surface Atlantic waters (0.009 µg/kg). Mean contents (ppm) in other materials included: ultramafic rocks, 0.8; basalts, 1.7; silicic rocks, 2.5; red clays, 3.4; amphibolites, 1.2. Oceanic ferromanganese deposits contained from 0.2 to 5.8 ppm; tin and cobalt contents were correlated.

Estensione dell'Abstraction Layer di DTNperf alle API di IBR-DTN

Sono dette “challenged networks” quelle reti in cui lunghi ritardi, frequenti partizionamenti e interruzioni, elevati tassi di errore e di perdita non consentono l’impiego dei classici protocolli di comunicazione di Internet, in particolare il TCP/IP. Il Delay-/Disruption-Tolerant Networking (DTN) è una soluzione per il trasferimento di dati attraverso queste reti. L’architettura DTN prevede l’introduzione, sopra il livello di trasporto, del cosiddetto “bundle layer”, che si occupa di veicolare messaggi, o bundle, secondo l’approccio store-and-forward: ogni nodo DTN conserva persistentemente un bundle finché non si presenta l’opportunità di inoltrarlo al nodo successivo verso la destinazione. Il protocollo impiegato nel bundle layer è il Bundle Protocol, le cui principali implementazioni sono tre: DTN2, l’implementazione di riferimento; ION, sviluppata da NASA-JPL e più orientata alle comunicazioni spaziali; IBR-DTN, rivolta soprattutto a dispositivi embedded. Ciascuna di esse offre API che consentono la scrittura di applicazioni in grado di inviare e ricevere bundle. DTNperf è uno strumento progettato per la valutazione delle prestazioni in ambito DTN. La più recente iterazione, DTNperf_3, è compatibile sia con DTN2 che con ION nella stessa versione del programma, grazie all’introduzione di un “Abstraction Layer” che fornisce un’unica interfaccia per l’interazione con le diverse implementazioni del Bundle Protocol e che solo internamente si occupa di invocare le API specifiche dell’implementazione attiva. Obiettivo della tesi è estendere l’Abstraction Layer affinché supporti anche IBR-DTN, cosicché DTNperf_3 possa essere impiegato indifferentemente su DTN2, ION e IBR DTN. Il lavoro sarà ripartito su tre fasi: nella prima esploreremo IBR DTN e le sue API; nella seconda procederemo all’effettiva estensione dell’Abstraction Layer; nella terza verificheremo il funzionamento di DTNperf a seguito delle modifiche, sia in ambiente esclusivamente IBR-DTN, sia ibrido.

API de servicios web orientados a accesibilidad

Hoy en día vivimos en una sociedad en la que las tecnologías son accesibles para gran parte de la población y las cuales tienen como finalidad, entre otras cosas, facilitar la vida de las personas en la medida de lo posible. Este proyecto busca hacer uso de esas tecnologías para facilitar la accesibilidad a textos para cualquiera que pueda tener dificultades con ellos, en mayor o menor medida. La finalidad de nuestro proyecto no es crear la aplicación para el uso directo de las personas sino desarrollar los servicios, y el acceso a los mismos, que faciliten la implementación de estas aplicaciones. Aún así en este proyecto se crea una aplicación de ejemplo para Android, en la cual se hace uso de los servicios como muestra de un posible uso de los mismos. Para facilitar el acceso a estos servicios y la comprensión de los mismos, en este proyecto se crea también una API web en la cual quedan todos ellos explicados, como acceder a ellos, su descripción, ejemplos de llamadas y de resultados de las llamadas, en definitiva, todo lo que pueda ayudar a un desarrollador interesado en ellos a utilizarlos sin mayor problema. Las aplicaciones posibles de estos servicios son de lo mas extensas. Así, por ejemplo, en un dispositivo móvil, si un usuario está leyendo un libro y no entiende una palabra o le resulta bastante complicada, tan solo tendría que sacar el móvil, introducir la palabra en una aplicación que llamara a uno de nuestros servicios y obtener el resultado requerido de esa palabra, de forma rápida y cómoda. El proyecto queda dividido en tres partes: el desarrollo de los servicios de accesibilidad, la web de la API explicando cada uno de estos servicios y una aplicación Android de ejemplo de utilización.

Immunoregulatory soluble CTLA-4 modifies effector T cell responses in systemic lupus erythematosus

Acknowledgments This work was supported by Arthritis Research UK (Grant no. 19282). We are grateful to Dr. Nick Fluck for his invaluable support in recruiting patients for the study, and Mrs. Vivien Vaughan for her invaluable expertise in recruiting study participants and maintaining ethical documentation.

Implication de l'apoptose des cellules endothéliales dans la libération de nouveau(x) médiateur(s) soluble(s) actif(s) sur le microenvironnemnt vasculaire

Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.