The dehydrogenation reactions between LiH and organic amines for solid state hydrogen storage systems

Hydrogen is considered as an appealing alternative to fossil fuels in the pursuit of sustainable, secure and prosperous growth in the UK and abroad. However there exists a persisting bottleneck in the effective storage of hydrogen for mobile applications in order to facilitate a wide implementation of hydrogen fuel cells in the fossil fuel dependent transportation industry. To address this issue, new means of solid state chemical hydrogen storage are proposed in this thesis. This involves the coupling of LiH with three different organic amines: melamine, urea and dicyandiamide. In principle, thermodynamically favourable hydrogen release from these systems proceeds via the deprotonation of the protic N-H moieties by the hydridic metal hydride. Simultaneously hydrogen kinetics is expected to be enhanced over heavier hydrides by incorporating lithium ions in the proposed binary hydrogen storage systems. Whilst the concept has been successfully demonstrated by the results obtained in this work, it was observed that optimising the ball milling conditions is central in promoting hydrogen desorption in the proposed systems. The theoretical amount of 6.97 wt% by dry mass of hydrogen was released when heating a ball milled mixture of LiH and melamine (6:1 stoichiometry) to 320 °C. It was observed that ball milling introduces a disruption in the intermolecular hydrogen bonding network that exists in pristine melamine. This effect extends to a molecular level electron redistribution observed as a function of shifting IR bands. It was postulated that stable phases form during the first stages of dehydrogenation which contain the triazine skeleton. Dehydrogenation of this system yields a solid product Li2NCN, which has been rehydrogenated back to melamine via hydrolysis under weak acidic conditions. On the other hand, the LiH and urea system (4:1 stoichiometry) desorbed approximately 5.8 wt% of hydrogen, from the theoretical capacity of 8.78 wt% (dry mass), by 270 °C accompanied by undesirable ammonia and trace amount of water release. The thermal dehydrogenation proceeds via the formation of Li(HN(CO)NH2) at 104.5 °C; which then decomposes to LiOCN and unidentified phases containing C-N moieties by 230 °C. The final products are Li2NCN and Li2O (270 °C) with LiCN and Li2CO3 also detected under certain conditions. It was observed that ball milling can effectively supress ammonia formation. Furthermore results obtained from energetic ball milling experiments have indicated that the barrier to full dehydrogenation between LiH and urea is principally kinetic. Finally the dehydrogenation reaction between LiH and dicyandiamide system (4:1 stoichiometry) occurs through two distinct pathways dependent on the ball milling conditions. When ball milled at 450 RPM for 1 h, dehydrogenation proceeds alongside dicyandiamide condensation by 400 °C whilst at a slower milling speed of 400 RPM for 6h, decomposition occurs via a rapid gas desorption (H2 and NH3) at 85 °C accompanied by sample foaming. The reactant dicyandiamide can be generated by hydrolysis using the product Li2NCN.

Modelling and Optimization of Energy Management Strategies for Hybrid Vehicles

In the last decades the automotive sector has seen a technological revolution, due mainly to the more restrictive regulation, the newly introduced technologies and, as last, to the poor resources of fossil fuels remaining on Earth. Promising solution in vehicles’ propulsion are represented by alternative architectures and energy sources, for example fuel-cells and pure electric vehicles. The automotive transition to new and green vehicles is passing through the development of hybrid vehicles, that usually combine positive aspects of each technology. To fully exploit the powerful of hybrid vehicles, however, it is important to manage the powertrain’s degrees of freedom in the smartest way possible, otherwise hybridization would be worthless. To this aim, this dissertation is focused on the development of energy management strategies and predictive control functions. Such algorithms have the goal of increasing the powertrain overall efficiency and contextually increasing the driver safety. Such control algorithms have been applied to an axle-split Plug-in Hybrid Electric Vehicle with a complex architecture that allows more than one driving modes, including the pure electric one. The different energy management strategies investigated are mainly three: the vehicle baseline heuristic controller, in the following mentioned as rule-based controller, a sub-optimal controller that can include also predictive functionalities, referred to as Equivalent Consumption Minimization Strategy, and a vehicle global optimum control technique, called Dynamic Programming, also including the high-voltage battery thermal management. During this project, different modelling approaches have been applied to the powertrain, including Hardware-in-the-loop, and diverse powertrain high-level controllers have been developed and implemented, increasing at each step their complexity. It has been proven the potential of using sophisticated powertrain control techniques, and that the gainable benefits in terms of fuel economy are largely influenced by the chose energy management strategy, even considering the powerful vehicle investigated.

Green supercapacitive systems

This Ph.D. thesis addresses the challenging goal of integrating supercapacitive features in MFCs by sustainable materials and processes and valorizing wastes by their processing as key components of supercapacitors and MFCs. Three main research lines have been pursued: i) the development of green supercapacitors by exploiting natural polymers as binders and electrospun separators, ii) the improvement of the power output of MFCs by the external integration of commercial and green supercapacitors, and ii) the development of supercapacitive microbial fuel cells by the monolithic integration of supercapacitive features in MFCs. This Thesis is articulated in the following Sections. Chapter 1 introduce the energy-water nexus, highlights the role played by supercapacitors and MFCs in this context, and describes the main components, and processes in these devices.

Analisi delle prestazioni di elettrolizzatori tipo PEM

Le fonti di energia rinnovabili rappresentano una forma di energia indispensabile al sostentamento dell’attuale sistema produttivo mondiale. L’energia eolica e fotovoltaica ricoprono un ruolo fondamentale nel panorama rinnovabile, e portano con se l’inevitabile svantaggio derivato dall’impossibilita di controllare la fonte primaria di energia. I sistemi di accumulo ed immagazzinamento di energia assumeranno un ruolo strategico nel prossimo scenario energetico, in particolare nell’elaborato viene posta l’attenzione sui sistemi Power-to-Gas. La tecnologia Power-to-Gas consente di produrre gas ad alta potenza specifica (idrogeno o metano sintetico), usando elettricità proveniente da fonti rinnovabili. L’elettrolisi è il metodo più efficiente per convertire energia elettrica in idrogeno. Tra le varie tecnologie, gli elettrolizzatori di tipologia PEM (Proton Exchange Membrane), sono considerati i più adatti all’accoppiamento con fonti di energia rinnovabile, per via della loro risposta alle variazioni di carico e dell’ampio campo di funzionamento. Il lavoro di tesi si concentra sull’analisi delle prestazioni di elettrolizzatori tipo PEM, ed in particolare sull’elettrolizzatore inserito all’interno del “Laboratorio di Microreti di Generazione ed Accumulo” del Tecnopolo di Ravenna. Il laboratorio ha lo scopo di studiare e testare sistemi per la produzione di energia elettrica da fonte rinnovabile e per l’accumulo. L’impianto è costituito principalmente da due pannelli fotovoltaici con il compito di produrre energia, due batterie per accumulare l’energia prodotta dai pannelli, un elettrolizzatore e tre bombole a idruri metallici per lo stoccaggio di idrogeno. Dai dati sperimentali ottenuti dalle prove in laboratorio si è ricavato un modello matematico black-box dell’elettrolizzatore. Il modello gestisce le equazioni della curva caratteristica (P;η). In seguito il modello ottenuto è stato confrontato con un caso analogo presente in letteratura.

Impiego dell’idrogeno per la sostenibilità delle flotte del Trasporto Pubblico Locale

La domanda mondiale di energia è in costante aumento e le attuali tecnologie per la produzione di energia dai combustibili fossili emettono anidride carbonica (CO2). La combinazione di idrogeno ed elettricità è un’incoraggiante soluzione verso la realizzazione di un futuro a “zero emissioni” basato sull’energia sostenibile. L’idrogeno molecolare è un elemento scarso in natura; la sua produzione è quasi esclusivamente da fonti fossili. Se prodotto tramite elettrolisi da fonti di energia naturali è possibile produrre idrogeno senza significative emissioni di anidride carbonica ma con costi ancora troppo elevati; tali metodologie al giorno d’oggi sono ancora poco sviluppate e non in grado di competere con le tecniche industriali più consolidate di derivazione dell’ idrogeno dalle fonti fossili. Un altro ostacolo risiede nella difficoltà di immagazzinarlo e trasportarlo; viene stoccato con sicurezza in grandi contenitori industriali o in recipienti ad alta pressione. Occorre garantire una sufficiente capacità di stoccaggio nelle applicazioni per autoveicoli, così da ottenere un buon equilibrio tra autonomia di guida e spazio di stoccaggio. Nell’autotrazione possono essere utilizzate le fuel cells che assicurano un uso efficiente dell’idrogeno; convertono l’energia chimica dell’idrogeno in energia elettrica, acqua e calore, assicurando rendimenti di conversione energetica molto alti, oltre a garantire una notevole silenziosità dovuta essenzialmente all’assenza di organi rotanti. Le fuel cells possono essere applicate anche ai veicoli dedicati al trasporto pubblico locale, garantendo l’abbattimento delle emissioni nocive nelle aeree urbane al fine del benessere dei cittadini. Tper è da anni attiva sul fronte della mobilità sostenibile; vanta una delle flotte di autobus più “verdi” d’Italia e in un futuro molto prossimo incrementerà ancora di più la percentuale di autobus a basse emissioni puntando soprattutto all’acquisto di autobus ad idrogeno.

Controllo emissioni MCI alimentati ad idrogeno

Il tema principale della tesi sono le emissioni di motori a combustione interna alimentati ad idrogeno. Dopo un'introduzione inziale, nella quale si spiegano le proprietà dell'idrogeno e i passaggi per ottenerlo, si entra nello specifico utilizzo di esso come combustibile e nelle modifiche da apportare ad un comune MCI. Nella parte centrale della tesi vengono prese in considerazione le anomalie di combustione ed alcune soluzioni per esse, soffermandosi in particolare sulla detonazione. Nella parte finale, invece, vengono trattate le emissioni inquinanti e i sistemi di post-trattamento dei gas di scarico, cercando di individuare soluzioni ottimali. Anche quando ci si concentra su altri aspetti però si pone sempre un occhio di riguardo alle possibili emissioni inquinanti dettate dalle condizioni descritte.

Sistemi di testing per celle a combustibile

La tesi tratta funzionamento, ottimizzazione e applicazioni delle celle a combustibile PEM (PEM Fuel cells) che sono dispositivi capaci di convertire reversibilmente l’energia chimica contenuta nel combustibile in energia elettrica, energia termica e prodotti di reazione. Vengono analizzati gli effetti di temperatura, pressione e umidità sulla cinetica, sulle prestazioni, sull’OCV, sulla conduttività della membrana e sul trasferimento di massa. In generale, per utilizzare una cella a combustibile PEM, ogni componente, materiale e l'assemblaggio delle celle dovrebbe essere realizzabile e ottimizzato per ottenere alte prestazioni. Vengono, quindi, trattate le tecniche di test e diagnosi che rappresentano il modo più popolare e affidabile per convalidare i progetti di questi componenti e della cella combustibile stessa. Inoltre, si affronta il discorso sull’idrogeno definito come vettore di energia che ha assunto un ruolo di primo piano per un mercato a basse emissioni; infatti ha un grande potenziale come combustibile alternativo e assume un ruolo centrale nello scenario energetico del futuro. Infine, si parla anche di applicazioni pratiche ed esistenti riguardanti le celle a combustibile in veicoli, come le proposte di Nuvera ed EH Group.

Rapid activation of Na+/H+ exchange by aldosterone in renal epithelial cells requires Ca2+ and stimulation of a plasma membrane proton conductance.

There is increasing evidence for an additional acute, nongenomic action of the mineralocorticoid hormone aldosterone on renal epithelial cells, leading to a two-step model of mineralocorticoid action on electrolyte excretion. We investigated the acute effect of aldosterone on intracellular free Ca2+ and on intracellular pH in an aldosterone-sensitive Madin-Darby canine kidney cell clone. Within seconds of application of aldosterone, but not of the glucocorticoid hydrocortisone, there was a 3-fold sustained increase of intracellular Ca2+ at a half-maximal concentration of 10(-10) mol/liter. Omission of extracellular Ca2+ prevented this hormone response. In the presence of extracellular Ca2+ aldosterone led to intracellular alkalinization. The Na+/H+ exchange inhibitor ethyl-isopropanol-amiloride (EIPA) prevented the aldosterone-induced alkalinization but not the aldosterone-induced increase of intracellular Ca2+. Omission of extracellular Ca2+ also prevented aldosterone-induced alkalinization. Instead, aldosterone led to a Zn(2+)-dependent intracellular acidification in the presence of EIPA, indicative of an increase of plasma membrane proton conductance. Under control conditions, Zn2+ prevented the aldosterone-induced alkalinization completely. We conclude that aldosterone stimulated net-entry of Ca2+ from the extracellular compartment and a plasma membrane H+ conductance as prerequisites for the stimulation of plasma membrane Na+/H+ exchange which in turn modulates K+ channel acitivity. It is probable that the aldosterone-sensitive H+ conductance maintains Na+/H+ exchange activity by providing an acidic environment in the vicinity of the exchanger. Thus, genomic action of aldosterone determines cellular transport equipment, whereas the nongenomic action regulates transporter activity that requires responses within seconds or minutes, which explains the rapid effects on electrolyte excretion.

Antisense-mediated inhibition of the plasma membrane Calcium-ATPase suppresses proliferation of MCF-7 cells

Alterations in Ca2+ signaling may contribute to tumorigenesis and the mechanism of action of some anticancer drugs. The plasma membrane calcium-ATPase (PMCA) is a crucial controller of intracellular Ca2+ signaling. Altered PMCA expression occurs in the mammary gland during lactation and in breast cancer cell lines. Despite this, the consequences of PMCA inhibition in breast cancer cell lines have not been investigated. In this work, we used Tet-off PMCA antisense-expressing MCF-7 cells to assess the effects of PMCA inhibition in a human breast cancer cell line. At a level of PMCA inhibition that did not completely prevent PMCA-mediated Ca2+ efflux and did not induce cell death, a dramatic inhibition of cellular proliferation was observed. Fluorescence-activated cell sorting analysis indicated that PMCA antisense involves changes in cell cycle kinetics but not cell cycle arrest. We concluded that modulation of PMCA has important effects in regulating the proliferation of human breast cancer MCF-7 cells.

Phosphorylation and membrane dissociation of the ARF exchange factor GBF1 in mitosis

Secretory protein trafficking is arrested and the Golgi apparatus fragmented when mammalian cells enter mitosis. These changes are thought to facilitate cell cycle progression and Golgi inheritance, and are brought about through the actions of mitotically active protein kinases. To better understand how the Golgi apparatus undergoes mitotic fragmentation we have sought to identify novel Golgi targets for mitotic kinases. We report here the identification of the ARF exchange factor GBF1 as a Golgi phosphoprotein. GBF1 is phosphorylated by CDK1-cyclin B in mitosis, which results in its dissociation from Golgi membranes. Consistent with a reduced level of GBF1 activity at the Golgi membrane there is a reduction in levels of membrane-associated GTP-bound ARF in mitotic cells. Despite the reduced levels of membrane bound GBF1 and ARF, COPI binding to the Golgi membrane appears unaffected in mitotic cells. Surprisingly, this pool of COPI is dependent upon GBF1 for its recruitment to the membrane, suggesting a low level of GBF1 activity persists in mitosis. We propose that the phosphorylation and membrane dissociation of GBF1 and the consequent reduction in ARF-GTP levels in mitosis are important for changes in Golgi dynamics and possibly other mitotic events mediated through effectors other than the COPI vesicle coat.

Characterisation Of The Membrane Transport Of Pilocarpine In Cell Suspension Cultures Of Pilocarpus Microphyllus.

Pilocarpine is an alkaloid obtained from the leaves of Pilocarpus genus, with important pharmaceutical applications. Previous reports have investigated the production of pilocarpine by Pilocarpus microphyllus cell cultures and tried to establish the alkaloid biosynthetic route. However, the site of pilocarpine accumulation inside of the cell and its exchange to the medium culture is still unknown. Therefore, the aim of this study was to determine the intracellular accumulation of pilocarpine and characterise its transport across membranes in cell suspension cultures of P. microphyllus. Histochemical analysis and toxicity assays indicated that pilocarpine is most likely stored in the vacuoles probably to avoid cell toxicity. Assays with exogenous pilocarpine supplementation to the culture medium showed that the alkaloid is promptly uptaken but it is rapidly metabolised. Treatment with specific ABC protein transporter inhibitors and substances that disturb the activity of secondary active transporters suppressed pilocarpine uptake and release suggesting that both proteins may participate in the traffic of pilocarpine to inside and outside of the cells. As bafilomicin A1, a specific V-type ATPase inhibitor, had little effect and NH4Cl (induces membrane proton gradient dissipation) had moderate effect, while cyclosporin A and nifedipine (ABC proteins inhibitors) strongly inhibited the transport of pilocarpine, it is believed that ABC proteins play a major role in the alkaloid transport across membranes but it is not the exclusive one. Kinetic studies supported these results.

Fermentation of Groundnut Shell Enzymatic Hydrolysate for Fuel Ethanol Production by Free and Sorghum Stalks Immobilized Cells of Pichia stipitis NCIM 3498

Groundnut shell (GS), after separation of pod, is readily available as a potential feedstock for production of fermentable sugars. The substrate was delignified with sodium sulfite. The delignified substrate released 670 mg/g of sugars after enzymatic hydrolysis (50 degrees C, 120 rpm, 50 hrs) using commercial cellulases (Dyadic Xylanase PLUS, Dyadic Inc. USA). The groundnut shell enzymatic hydrolysate (45.6 g/L reducing sugars) was fermented for ethanol production with free and sorghum stalks immobilized cells of Pichia stipitis NCIM 3498 under submerged cultivation conditions. Immobilization of yeast cells on sorghum stalks were confirmed by scanning electron microscopy (SEM). A maximum of ethanol production (17.83 g/L, yield 0.44 g/g and 20.45 g/L, yield 0.47 g/g) was observed with free and immobilized cells of P. stipitis respectively in batch fermentation conditions. Recycling of immobilized cells showed a stable ethanol production (20.45 g/L, yield 0.47 g/g) up to 5 batches followed by a gradual downfall in subsequent cycles.

Experimental and theoretical study of two-photon absorption in nitrofuran derivatives: Promising compounds for photochemotherapy

We report experimental and theoretical studies of the two-photon absorption spectrum of two nitrofuran derivatives: nitrofurantoine, (1-(5-nitro-2-furfurilideneamine)-hidantoine) and quinifuryl, 2-(5`-nitro-2`-furanyl) ethenyl-4-{N-[4`-(N,N-diethylamino)-1`-methylbutyl]carbamoyl} quinoline. Both molecules are representative of a family of 5-nitrofuran-ethenyl-quinoline drugs that have been demonstrated to display high toxicity to various species of transformed cells in the dark. We determine the two-photon absorption cross-section for both compounds, from 560 to 880 nm, which present peak values of 64 GM for quinifuryl and 20 GM for nitrofurantoine (1 GM = 1 x 10(-50) cm(4).s.photon(-1)). Besides, theoretical calculations employing the linear and quadratic response functions were carried out at the density functional theory level to aid the interpretations of the experimental results. The theoretical results yielded oscillator strengths, two-photon transition probabilities, and transition energies, which are in good agreement with the experimental data. A higher number of allowed electronic transitions was identified for quinifuryl in comparison to nitrofurantoine by the theoretical calculations. Due to the planar structure of both compounds, the differences in the two-photon absorption cross-section values are a consequence of their distinct conjugation lengths. (c) 2011 American Institute of Physics. [doi:10.1063/1.3514911]

Catecholamine release in heat-stressed Antarctic fish causes proton extrusion by the red cells

Two species of Antarctic fish were stressed by moving them from seawater at -1 degrees C to seawater at 10 degrees C and holding them for a period of 10 min. The active cryopelagic species Pagothenia borchgrevinki maintained heart rate while in the benthic species Trematomus bernacchii there was an increase in heart rate. Blood pressure did not change in either species. Both species released catecholamines into the circulation as a consequence of the stress. P. borchgrevinki released the greater amounts, having mean plasma concentrations of 177 +/- 54 nmol.l(-1) noradrenaline and 263 +/- 131 nmol.l(-1) adrenaline at 10 min. Pla.sma noradrenaline concentrations rose to 47 +/- 14 nmol.l(-1) and adrenaline to 73 +/- 28 nmol.l(-1) in T. bernacchii. Blood from P. borchgrevinki was tonometered in the presence of isoprenaline. A fall in extracellular pH suggests the presence of a Na+/H+ antiporter on the red cell membrane, the first demonstration of this in an Antarctic fish. Treatment with the beta-adrenergic antagonist drug sotalol inhibited swelling of red blood cells taken from temperature-stressed P. borchgrevinki, suggesting that the antiporter responds to endogenous catecholamines.

Elevated plasma membrane and sarcoplasmic reticulum Ca2+ pump mRNA levels in cultured aortic smooth muscle cells from spontaneously hypertensive rats

We have observed previously that Ca2+ pump-mediated Ca2+ efflux is elevated in cultured aortic smooth muscle cells from spontaneously hypertensive rats compared to those from Wistar-Kyoto rat controls. The objective of this work was to determine if these strains differ in mRNA levels for the PMCA1 isoform of the plasma membrane Ca2+-ATPase and the SERCA2 isoform of the sarcoplasmic reticulum Ca2+-ATPase. mRNA levels were compared in cultured aortic smooth muscle cells from 10-week-old male rats. PMCA1 and SERCA2 mRNA levels were elevated in SHR compared to WKY. Angiotensin II increased the level of PMCA1 and SERCA2 mRNA in both strains. These studies provide further evidence for alterered Ca2+ homeostasis in hypertension at the level of Ca2+ transporting ATPases in the spontaneously hypertensive rat model. These data are also consistent with the hypothesis that the expression of these two Ca2+ pumps may be linked. (C) 1997 Academic Press