Temporal patterns of the seagrass "Cymodocea nodosa" and depth-related patterns of the green algae "Caulerpa prolifera" in the Canarian Archipelago

Máster Oficial en Gestión Costera

Green Cloud Computing: una rassegna comparativa

La rapida crescita di Internet e del numero di host connessi sta portando sempre di più alla nascita di nuove forme di tecnlogie ed applicazioni serverside, facendo del client un thin-client. Il Cloud Computing offre una valida piattaforma a queste nuove tecnologie, ma esso si deve confrontare con diverse problematiche, fra cui la richiesta energetica sempre più crescente, che si ripercuote su un'inevitabile aumento dei gas serra prodotti indirettamente. In questa tesi analizzeremo i problemi energetici legati al Cloud Computing e le possibili soluzioni, andando infine a creare una tassonomia fra i diversi Cloud Computing più importanti sul mercato attuale.

Review of the efficacy of green tea, isoflavones and aloe vera supplements based on randomised controlled trials

We assess the evidence for health benefits of three commonly consumed plant food supplements (PFS), green tea, isoflavone and aloe vera, based on published systematic reviews of randomised controlled trials (RCTs). Whilst the potential benefits of green tea have been reported in a wide range of health areas, it is only in the area of the metabolic syndrome that the number of RCTs is approaching sufficient to judge such efficacy. Isoflavone supplements are widely used, and RCTs indicate that they affect bone resorption at lower doses in postmenopausal women undergoing estrogen-related bone loss, but this is only translated to attenuation of bone loss at higher doses of isoflavones A systematic review on RCTs concluded that the effects of isoflavones

Green information technology

Quando si parla di green information technology si fa riferimento a un nuovo filone di ricerche focalizzate sulle tecnologie ecologiche o verdi rivolte al rispetto ambientale. In prima battuta ci si potrebbe chiedere quali siano le reali motivazioni che possono portare allo studio di tecnologie green nel settore dell’information technology: sono così inquinanti i computer? Non sono le automobili, le industrie, gli aerei, le discariche ad avere un impatto inquinante maggiore sull’ambiente? Certamente sì, ma non bisogna sottovalutare l’impronta inquinante settore IT; secondo una recente indagine condotta dal centro di ricerche statunitense Gartner nel 2007, i sistemi IT sono tra le maggiori fonti di emissione di CO2 e di altri gas a effetto serra , con una percentuale del 2% sulle emissioni totali del pianeta, eguagliando il tasso di inquinamento del settore aeromobile. Il numero enorme di computer disseminato in tutto il mondo assorbe ingenti quantità di energia elettrica e le centrali che li alimentano emettono tonnellate di anidride carbonica inquinando l’atmosfera. Con questa tesi si vuole sottolineare l’impatto ambientale del settore verificando, attraverso l’analisi del bilancio sociale ed ambientale, quali misure siano state adottate dai leader del settore informatico. La ricerca è volta a dimostrare che le più grandi multinazionali informatiche siano consapevoli dell’inquinamento prodotto, tuttavia non adottano abbastanza soluzioni per limitare le emissioni, fissando futili obiettivi futuri.

Nuovi processi "green" per la funzionalizzazione di composti fenolici.

L’obiettivo di questo lavoro è lo studio della funzionalizzazione del fenolo mediante vie sintetiche “green”, che utilizzino quindi reagenti non clorurati e catalizzatori eterogenei, quindi facilmente recuperabili e riutilizzabili. Esistono però altri derivati fenolici di interesse commerciale, quali il catecolo, in quanto reagente di partenza per svariate molecole (tra cui appunto il DOPET) utilizzate in vari ambiti applicativi (alimentare, cosmetica, farmaceutica, agrochimica). In particolare, lo studio è stato focalizzato sulla sintesi dell’IDROSSITIROSOLO (o DOPET). Le prove effettutate con fenolo non hanno portato alla formazione del composto desiderato, ma di altri prodotti che comunque hanno interesse commerciale; ad esempio, è stato ottenuto il 2-fenossietanolo con elevata resa e selettività. Oltre al fenolo, ho studiato la reattività del metilendiossobenzene; con entrambi è stato ottenuto (seppur con basse rese) l’attacco all’anello da parte dell’etil gliossilato, formando così un intermedio potenzialmente utile per la sintesi dell’idrossitirosolo.

Physiology and Biotechnology of the Hydrogen Production with the Green Microalga Chlamydomonas reinhardtii

The hydrogen production in the green microalga Chlamydomonas reinhardtii was evaluated by means of a detailed physiological and biotechnological study. First, a wide screening of the hydrogen productivity was done on 22 strains of C. reinhardtii, most of which mutated at the level of the D1 protein. The screening revealed for the first time that mutations upon the D1 protein may result on an increased hydrogen production. Indeed, productions ranged between 0 and more than 500 mL hydrogen per liter of culture (Torzillo, Scoma et al., 2007a), the highest producer (L159I-N230Y) being up to 5 times more performant than the strain cc124 widely adopted in literature (Torzillo, Scoma, et al., 2007b). Improved productivities by D1 protein mutants were generally a result of high photosynthetic capabilities counteracted by high respiration rates. Optimization of culture conditions were addressed according to the results of the physiological study of selected strains. In a first step, the photobioreactor (PBR) was provided with a multiple-impeller stirring system designed, developed and tested by us, using the strain cc124. It was found that the impeller system was effectively able to induce regular and turbulent mixing, which led to improved photosynthetic yields by means of light/dark cycles. Moreover, improved mixing regime sustained higher respiration rates, compared to what obtained with the commonly used stir bar mixing system. As far as the results of the initial screening phase are considered, both these factors are relevant to the hydrogen production. Indeed, very high energy conversion efficiencies (light to hydrogen) were obtained with the impeller device, prooving that our PBR was a good tool to both improve and study photosynthetic processes (Giannelli, Scoma et al., 2009). In the second part of the optimization, an accurate analysis of all the positive features of the high performance strain L159I-N230Y pointed out, respect to the WT, it has: (1) a larger chlorophyll optical cross-section; (2) a higher electron transfer rate by PSII; (3) a higher respiration rate; (4) a higher efficiency of utilization of the hydrogenase; (5) a higher starch synthesis capability; (6) a higher per cell D1 protein amount; (7) a higher zeaxanthin synthesis capability (Torzillo, Scoma et al., 2009). These information were gathered with those obtained with the impeller mixing device to find out the best culture conditions to optimize productivity with strain L159I-N230Y. The main aim was to sustain as long as possible the direct PSII contribution, which leads to hydrogen production without net CO2 release. Finally, an outstanding maximum rate of 11.1 ± 1.0 mL/L/h was reached and maintained for 21.8 ± 7.7 hours, when the effective photochemical efficiency of PSII (ΔF/F'm) underwent a last drop to zero. If expressed in terms of chl (24.0 ± 2.2 µmoles/mg chl/h), these rates of production are 4 times higher than what reported in literature to date (Scoma et al., 2010a submitted). DCMU addition experiments confirmed the key role played by PSII in sustaining such rates. On the other hand, experiments carried out in similar conditions with the control strain cc124 showed an improved final productivity, but no constant PSII direct contribution. These results showed that, aside from fermentation processes, if proper conditions are supplied to selected strains, hydrogen production can be substantially enhanced by means of biophotolysis. A last study on the physiology of the process was carried out with the mutant IL. Although able to express and very efficiently utilize the hydrogenase enzyme, this strain was unable to produce hydrogen when sulfur deprived. However, in a specific set of experiments this goal was finally reached, pointing out that other than (1) a state 1-2 transition of the photosynthetic apparatus, (2) starch storage and (3) anaerobiosis establishment, a timely transition to the hydrogen production is also needed in sulfur deprivation to induce the process before energy reserves are driven towards other processes necessary for the survival of the cell. This information turned out to be crucial when moving outdoor for the hydrogen production in a tubular horizontal 50-liter PBR under sunlight radiation. First attempts with laboratory grown cultures showed that no hydrogen production under sulfur starvation can be induced if a previous adaptation of the culture is not pursued outdoor. Indeed, in these conditions the hydrogen production under direct sunlight radiation with C. reinhardtii was finally achieved for the first time in literature (Scoma et al., 2010b submitted). Experiments were also made to optimize productivity in outdoor conditions, with respect to the light dilution within the culture layers. Finally, a brief study of the anaerobic metabolism of C. reinhardtii during hydrogen oxidation has been carried out. This study represents a good integration to the understanding of the complex interplay of pathways that operate concomitantly in this microalga.

Design and development of new green catalytic methodologies for the synthesis of enantiomerically enriched molecules

The following Ph.D work was mainly focused on catalysis, as a key technology, to achieve the objectives of sustainable (green) chemistry. After introducing the concepts of sustainable (green) chemistry and an assessment of new sustainable chemical technologies, the relationship between catalysis and sustainable (green) chemistry was briefly discussed and illustrated via an analysis of some selected and relevant examples. Afterwards, as a continuation of the ongoing interest in Dr. Marco Bandini’s group on organometallic and organocatalytic processes, I addressed my efforts to the design and development of novel catalytic green methodologies for the synthesis of enantiomerically enriched molecules. In the first two projects the attention was focused on the employment of solid supports to carry out reactions that still remain a prerogative of omogeneous catalysis. Firstly, particular emphasis was addressed to the discovery of catalytic enantioselective variants of nitroaldol condensation (commonly termed Henry reaction), using a complex consisting in a polyethylene supported diamino thiopene (DATx) ligands and copper as active species. In the second project, a new class of electrochemically modified surfaces with DATx palladium complexes was presented. The DATx-graphite system proved to be efficient in promoting the Suzuki reaction. Moreover, in collaboration with Prof. Wolf at the University of British Columbia (Vancouver), cyclic voltammetry studies were reported. This study disclosed new opportunities for carbon–carbon forming processes by using heterogeneous, electrodeposited catalyst films. A straightforward metal-free catalysis allowed the exploration around the world of organocatalysis. In fact, three different and novel methodologies, using Cinchona, Guanidine and Phosphine derivatives, were envisioned in the three following projects. An interesting variant of nitroaldol condensation with simple trifluoromethyl ketones and also their application in a non-conventional activation of indolyl cores by Friedel-Crafts-functionalization, led to two novel synthetic protocols. These approaches allowed the preparation of synthetically useful trifluoromethyl derivatives bearing quaternary stereocenters. Lastly, in the sixth project the first γ-alkylation of allenoates with conjugated carbonyl compounds was envisioned. In the last part of this Ph.D thesis bases on an extra-ordinary collaboration with Prof. Balzani and Prof. Gigli, I was involved in the synthesis and characterization of a new type of heteroleptic cyclometaled-Ir(III) complexes, bearing bis-oxazolines (BOXs) as ancillary ligands. The new heteroleptic complexes were fully characterized and in order to examine the electroluminescent properties of FIrBOX(CH2), an Organic Light Emitting Device was realized.

Use of solvents and environmental friendly materials for applications in Green Chemistry

The present Thesis studies three alternative solvent groups as sustainable replacement of traditional organic solvents. Some aspects of fluorinated solvents, supercritical fluids and ionic liquids, have been analysed with a critical approach and their effective “greenness” has been evaluated from the points of view of the synthesis, the properties and the applications. In particular, the attention has been put on the environmental and human health issues, evaluating the eco-toxicity, the toxicity and the persistence, to underline that applicability and sustainability are subjects with equal importance. The “green” features of fluorous solvents and supercritical fluids are almost well-established; in particular supercritical carbon dioxide (scCO2) is probably the “greenest” solvent among the alternative solvent systems developed in the last years, enabling to combine numerous advantages both from the point of view of industrial/technological applications and eco-compatibility. In the Thesis the analysis of these two classes of alternative solvents has been mainly focused on their applicability, rather than the evaluation of their environmental impact. Specifically they have been evaluated as alternative media for non-aqueous biocatalysis. For this purpose, the hydrophobic ion pairing (HIP), which allows solubilising enzymes in apolar solvents by an ion pairing between the protein and a surfactant, has been investigated as effective enzymatic derivatisation technique to improve the catalytic activity under homogeneous conditions in non conventional media. The results showed that the complex enzyme-surfactant was much more active both in fluorous solvents and in supercritical carbon dioxide than the native form of the enzyme. Ionic liquids, especially imidazolium salts, have been proposed some years ago as “fully green” alternative solvents; however this epithet does not take into account several “brown” aspects such as their synthesis from petro-chemical starting materials, their considerable eco-toxicity, toxicity and resistance to biodegradation, and the difficulty of clearly outline applications in which ionic liquids are really more advantageous than traditional solvents. For all of these reasons in this Thesis a critical analysis of ionic liquids has been focused on three main topics: i) alternative synthesis by introducing structural moieties which could reduce the toxicity of the most known liquid salts, and by using starting materials from renewable resources; ii) on the evaluation of their environmental impact through eco-toxicological tests (Daphnia magna and Vibrio fischeri acute toxicity tests, and algal growth inhibition), toxicity tests (MTT test, AChE inhibition and LDH release tests) and fate and rate of aerobic biodegradation in soil and water; iii) and on the demonstration of their effectiveness as reaction media in organo-catalysis and as extractive solvents in the recovery of vegetable oil from terrestrial and aquatic biomass. The results about eco-toxicity tests with Daphnia magna, Vibrio fischeri and algae, and toxicity assay using cultured cell lines, clearly indicate that the difference in toxicity between alkyl and oxygenated cations relies in differences of polarity, according to the general trend of decreasing toxicity by decreasing the lipophilicity. Independently by the biological approach in fact, all the results are in agreement, showing a lower toxicity for compounds with oxygenated lateral chains than for those having purely alkyl lateral chains. These findings indicate that an appropriate choice of cation and anion structures is important not only to design the IL with improved and suitable chemico-physical properties but also to obtain safer and eco-friendly ILs. Moreover there is a clear indication that the composition of the abiotic environment has to be taken into account when the toxicity of ILs in various biological test systems is analysed, because, for example, the data reported in the Thesis indicate a significant influence of salinity variations on algal toxicity. Aerobic biodegradation of four imidazolium ionic liquids, two alkylated and two oxygenated, in soil was evaluated for the first time. Alkyl ionic liquids were shown to be biodegradable over the 6 months test period, and in contrast no significant mineralisation was observed with oxygenated derivatives. A different result was observed in the aerobic biodegradation of alkylated and oxygenated pyridinium ionic liquids in water because all the ionic liquids were almost completely degraded after 10 days, independently by the number of oxygen in the lateral chain of the cation. The synthesis of new ionic liquids by using renewable feedstock as starting materials, has been developed through the synthesis of furan-based ion pairs from furfural. The new ammonium salts were synthesised in very good yields, good purity of the products and wide versatility, combining low melting points with high decomposition temperatures and reduced viscosities. Regarding the possible applications as surfactants and biocides, furan-based salts could be a valuable alternative to benzyltributylammonium salts and benzalkonium chloride that are produced from non-renewable resources. A new procedure for the allylation of ketones and aldehydes with tetraallyltin in ionic liquids was developed. The reaction afforded high yields both in sulfonate-containing ILs and in ILs without sulfonate upon addition of a small amount of sulfonic acid. The checked reaction resulted in peculiar chemoselectivity favouring aliphatic substrates towards aromatic ketones and good stereoselectivity in the allylation of levoglucosenone. Finally ILs-based systems could be easily and successfully recycled, making the described procedure environmentally benign. The potential role of switchable polarity solvents as a green technology for the extraction of vegetable oil from terrestrial and aquatic biomass has been investigated. The extraction efficiency of terrestrial biomass rich in triacylglycerols, as soy bean flakes and sunflower seeds, was comparable to those of traditional organic solvents, being the yield of vegetable oils recovery very similar. Switchable polarity solvents as been also exploited for the first time in the extraction of hydrocarbons from the microalga Botryococcus braunii, demonstrating the efficiency of the process for the extraction of both dried microalgal biomass and directly of the aqueous growth medium. The switchable polarity solvents exhibited better extraction efficiency than conventional solvents, both with dried and liquid samples. This is an important issue considering that the harvest and the dewatering of algal biomass have a large impact on overall costs and energy balance.

Green Network - Un progetto urbano per lo scalo San Donato a Bologna

Da alcuni anni Bologna è interessata da un processo di trasformazione,che investe l’economia, la società e la città fisica. Le mutazioni delle condizioni tecnologiche, economiche e ambientali inducono trasformazioni nel modo di concepire la pianificazione. In questo contesto di trasformazioni gli spazi vuoti si offrono come straordinaria risorsa di nuove opportunità progettuali in termini di qualità urbana, inoltre si pongono come occasione per avviare una seria politica di sostenibilità in grado di ridisegnare una città più attrattiva ed efficiente nei suoi servizi. La probabile prossima dismissione dello scalo merci San Donato si presenta quindi come concreta possibilità d’intervento in un’area periurbana diventata ormai vera e propria centralità.

L'utilizzo di carbonati come reagenti per la sintesi "green" di derivati fenolici: l'esempio del 2-fenossi-1-etanolo

2-Phenoxyethanol (ethylene glycol monophenyl ether) is used as solvent for cellulose acetate, dyes, inks, and resins; it is a synthetic intermediate in the production of plasticizers, pharmaceuticals, and fragrances. Phenoxyethanol is obtained industrially by reaction of phenol with ethylene oxide, in the presence of an homogeneous alkaline catalyst, typically sodium hydroxide. The yield is not higher than 95-96%, because of the formation of polyethoxylated compounds. However, the product obtained may not be acceptable for use in cosmetic preparations and fragrance formulations, due to presence of a pungent “metallic” odor which masks the pleasant odor of the ether, deriving from residual traces of the metallic catalyst. Here we report a study aimed at using ethylene carbonate in place of ethylene oxide as the reactant for phenoxyethanol synthesis; the use of carbonates as green nucleophilic reactants is an important issue in the context of a modern and sustainable chemical industry. Moreover, in the aim of developing a process which might adhere the principles of Green Chemistry, we avoided the use of solvents, and used heterogeneous basic catalysts. We carried out the reaction by using various molar ratios between phenol and ethylene carbonate, at temperatures ranging between 180 and 240°C, with a Na-mordenite catalyst. Under specific conditions, it was possible to obtain total phenol conversion with >99% yield to phenoxyethanol in few hours reaction time, using a moderate excess of ethylene carbonate. Similar results, but with longer reaction times, were obtained using a stoichiometric feed ratio of reactants. One important issue of the research was finding conditions under which the leaching of Na was avoided, and the catalyst could be separated and reused for several reaction batches.

The Green Way - Principi di sostenibilità nel progetto urbanistico - Alcune Riflessioni

L’obiettivo della presente tesi curriculare è una lettura, in chiave critica, di alcuni esami ed esperienze significative svolte all’interno del corso di studi presso la Facoltà di Architettura “Aldo Rossi”. Questa tesi è caratterizzata da riflessioni circa i principi di sostenibilità per il progetto urbanistico: partendo dal concetto di sostenibilità, si procederà nel rivedere le tappe fondamentali della nascita di questo termine, analizzare gli impegni sottoscritti a livello mondiale ed infine valutare come tali principi sono stati trattati lungo il percorso di studi intrapreso: nel Laboratorio di Sintesi Finale in Architettura Sostenibile, nel Laboratorio di Urbanistica e durante il corso di Tecnica Urbanistica, con riferimento all’esperienza IP Socrates Erasmus Intensive Programme svolto presso la University of Western England a Bristol. Ognuno tra i progetti scelti per questa tesi curriculare è caratterizzato dalla presenza di “verde” come elemento unificatore. Il verde è una componente essenziale nelle nostre città e la qualità ambientale fa parte dei principi cardini dello sviluppo sostenibile; da qui il titolo “the green way”, verde come impronta ecologica, verde come parte integrante del progetto e verde come principio alla base di un una nuova mentalità sostenibile.

Sustainable inorganic Binders and Their Applications in Building Engineering: A Green Alternative to Ordinary Portland Cement

In the last decades, the building materials and construction industry has been contributing to a great extent to generate a high impact on our environment. As it has been considered one of the key areas in which to operate to significantly reduce our footprint on environment, there has been widespread belief that particular attention now has to be paid and specific measures have to be taken to limit the use of non-renewable resources.The aim of this thesis is therefore to study and evaluate sustainable alternatives to commonly used building materials, mainly based on ordinary Portland Cement, and find a supportable path to reduce CO2 emissions and promote the re-use of waste materials. More specifically, this research explores different solutions for replacing cementitious binders in distinct application fields, particularly where special and more restricting requirements are needed, such as restoration and conservation of architectural heritage. Emphasis was thus placed on aspects and implications more closely related to the concept of non-invasivity and environmental sustainability. A first part of the research was addressed to the study and development of sustainable inorganic matrices, based on lime putty, for the pre-impregnation and on-site binding of continuous carbon fiber fabrics for structural rehabilitation and heritage restoration. Moreover, with the aim to further limit the exploitation of non-renewable resources, the synthesis of chemically activated silico-aluminate materials, as metakaolin, ladle slag or fly ash, was thus successfully achieved. New sustainable binders were hence proposed as novel building materials, suitable to be used as primary component for construction and repair mortars, as bulk materials in high-temperature applications or as matrices for high-toughness fiber reinforced composites.