Biokerosene from coconut, babassu, camelina and palm kernel oils: production and properties of their blends with fossil kerosene

On December 20th 2006 the European Commission approved a law proposal to include the civil aviation sector in the European market of carbon dioxide emission rights [European Union Emissions Trading System, EUETS). On July 8th 2009, the European Parliament and Conseil agreed that all flights leaving or landing in the EU airports starting from January 1st 2012 should be included in the EUETS. On November 19th 2008, the EU Directive 2008/101/CE [1] included the civil aviation activities in the EUETS, and this directive was transposed by the Spanish law 13/2010 of July 5th 2010 [2]. Thus, in 2012 the aviation sector should reduce their emissions to 97 % of the mean values registered in the period 2004-2006, and for 2013 these emission reductions should reach 95 % of the mean values for that same period. Trying to face this situation, the aviation companies are planning seriously the use of alternative jet fuels to reduce their greenhouse gas emissions and to lower their costs. However, some US airlines have issued a lawsuit before the European Court of Justice based in that this EU action violates a long standing worldwide aviation treaty, the Chicago convention of 1944, and also the Chinese aviation companies have rejected to pay any EU carbon dioxide tax [3]. Moreover, the USA Departments of Agriculture and Energy and the Navy will invest a total of up to $150 million over three years to spur production of aviation and marine biofuels for commercial and military applications [4]. However, the jet fuels should fulfill a set of extraordinarily sensitive properties to guarantee the safety of planes and passengers during all the flights.

Cross-dehydrogenative coupling reaction using copper oxide impregnated on magnetite in deep eutectic solvents

The synthesis of different tetrahydroisoquinolines using choline chloride : ethylene glycol as a deep eutectic solvent (DES) and copper(II) oxide impregnated on magnetite as a catalyst has been accomplished successfully. The copper catalyst amount is the lowest loading ever reported. The presence of DES showed to be essential since the reaction in the absence of this medium did not proceed. A direct proportional relationship was found between the conductivity of DES medium and the yield obtained. The DES and the catalyst could be reused up to ten times without any detrimental effect on the yield of the reaction, with the aerobic conditions making the protocol highly sustainable, where the only waste is water.

Surface X-ray studies of catalytic clean technologies

The rational design of new heterogeneous catalysts for clean chemical technologies can be accelerated by molecular level insight into surface chemical processes. In situ methodologies, able to provide time-resolved and/or pressure dependent information on the evolution of reacting adsorbed layers over catalytically relevant surfaces, are therefore of especial interest. Here we discuss recent applications of surface X-ray techniques to surface-catalysed oxidations, (de)hydrogenations, C-C coupling, dehalogenation and associated catalyst restructuring, and explore how these may help to shape future sustainable chemistry. © 2010 The Royal Society of Chemistry.

Hydrothermal saline promoted grafting:a route to sulfonic acid SBA-15 silica with ultra-high acid site loading for biodiesel synthesis

A simple grafting protocol is reported which affords a ten-fold enhancement in acid site density of mesoporous sulfonic acid silicas compared to conventional syntheses, offering improved process efficiency and new opportunities for tailored supported solid acids in sustainable chemistry. This journal is

Nanotechnology in the food industry I: applications

Nanotechnology is a multidisciplinary science that is having a boom today, providing new products with attractive physicochemical properties for many applications. In agri/feed/food sector, nanotechnology offers great opportunities for obtaining products and innovative applications for agriculture and livestock, water treatment and the production, processing, storage and packaging of food. To this end, a wide variety of nanomaterials, ranging from metals and inorganic metal oxides to organic nanomaterials carrying bioactive ingredients are applied. This review shows an overview of current and future applications of nanotechnology in the food industry. Food additives and materials in contact with food are now the main applications, while it is expected that in the future are in the field of nano-encapsulated and nanocomposites in applications as novel foods, additives, biocides, pesticides and materials food contact.

Microwave Synthesis of Short-Chained Fluorinated Ionic Liquids and Their Surface Properties

Microwave synthesis is shown to be a valuable route to novel fluorinated ionic liquid surfactants. 1-Methyl-3-(3,3,4,4,5,5,6,6,6-nonafluorohexyl)imidazolium iodide was prepared by treatment of 1-methylimidazole with 1-iodo-1H,1H,2H,2H-perfluorohexane in a microwave reactor, and this product underwent anion exchange to yield 1-methyl-3-(3,3,4,4,5,5,6,6,6-nonafluorohexyl)imidazolium nonafluoro-1-butanesulfonate. This catanionic surfactant showed intriguing phase behavior and low surface tension.

Selection of ionic liquids to be used as separation agents for terpenes and terpenoids

In this work, ionic liquids are evaluated for the first time as solvents for extraction and entrainers in separation processes involving terpenes and terpenoids. For that purpose, activity coefficients at infinite dilution, γ13 ∞, of terpenes and terpenoids, in the ionic liquids [C4mim]Cl, [C4mim][CH3SO3], [C4mim][(CH3)2PO4] and [C4mim][CF3SO3] were determined by gas−liquid chromatography at six temperatures in the range 398.15 to 448.15 K. On the basis of the experimental values, a correlation of γ13 ∞ with an increase of the solubility parameters is proposed. The infinite dilution thermodynamic functions were calculated showing the entropic effect is dominant over the enthalpic. Gas−liquid partition coefficients give indications about the recovery and purification of terpenes and terpenoids from ionic liquid solutions. Presenting a strong innovative character, COSMO-RS was evaluated for the description of the selectivities and capacities, showing to be a useful tool for the screening of ionic liquids in order to find suitable candidates for terpenes and terpenoids extraction, and separation. COSMO-RS predictions show that in order to achieve the maximum separation efficiency, polar anions should be used such as bis(2,4,4-trimethylpentyl)phosphinate or acetate, whereas high capacities require nonpolar cations such as phosphonium.

Synthesis of 3,5-Disubstituted Isoxazoles and Isoxazolines in Deep Eutectic Solvents

The synthesis of different 3,5-disubstituted isoxazoles and related isoxazolines using choline chloride:urea as deep eutectic solvent (DES) in a one-pot three step reaction has been accomplished successfully. The use of highly nucleophilic functionalized DES did not affect the process where highly electrophilic reagents or intermediates are involved. The presence of DES showed to be essential since the reaction in absence of this media did not proceed. The DES media could be reused up to five times without a detrimental effect on the yield of the reaction. To exemplify the synthetic potential of this methodology, the reaction was scaled up to the gram scale without any noticeable problem. Finally, different isoxazoles were easily transformed into β-aminoenones.

Mesoporous mixed Nb2O5-ZrO2 catalysts for dehydration of glucose into 5-hydroxymethylfurfural

Biomass is the world’s most important renewable carbon source, whose major component, carbohydrates, can be valorized by transformation into biofuels and high value-added chemicals. Among the latter, 5-hydroxymethylfurfural (HMF), obtained by C6 carbohydrates dehydration, is a versatile and key intermediate for the production of a large spectrum of biobased chemicals. Different catalytic systems have been evaluated for HMF production, mostly based on heterogeneous catalysis as alternative to the use of conventional mineral acids [1]. Moreover, niobium oxide has shown interesting properties as acid catalyst for dehydration of sugars [2-3]. On the other hand, the high surface area and large pore size of mesoporous solids make them suitable for many catalytic processes. In the present work, the dehydration of glucose to HMF has been evaluated by using different mesoporous mixed Nb2O5-ZrO2 in a biphasic water–Methyl Isobutyl Ketone (MIBK) solvent system to avoid the HMF degradation. Different experimental parameters, such as reaction temperature and time, as well as the addition of CaCl2 have been studied in order to maximize the HMF yield.N2 adsorption-desorption isotherms have corroborated the mesostructured character of catalysts, being all isotherms of Type IV according to the IUPAC classification. BET surface area decreases for catalysts with higher Zr content (Table 1). Likewise, pore volume and average pore diameter values diminish after Zr incorporation. Concerning the acid properties, a clear correlation between Nb and acidity can be observed, in such a way that total acidity, as deduced from NH3-TPD, decreases when the Zr content rises, and consequently the amount of Nb is reduced.These mesoporous Nb-Zr catalysts have been tested in the dehydration of glucose to HMF at 175 ºC under batch operation in aqueous solution, using MIBK as co-solvent. It can be observed that both glucose conversion and HMF yield increase with the Nb content, being maximum (90% and 36%, respectively) after 90 minutes for Nb2O5. This trend changes when CaCl2 is added to the reaction medium, improving the catalytic performance of mixed oxides and ZrO2, but Nb2O5 maintains similar results than without salt addition. This could be justified by the interaction between CaCl2 and Lewis acid sites, since zirconium oxide possesses a higher amount of this acid sites type.

Photocatalytic production of chemicals and hydrogen from biomass

In this work, with the aim to tackle several approaches towards sustainable chemistry, two reactions were studied: aerobic photo-oxidation of biomass derived 5-hydroxymethyl-2-furfural (HMF), and anaerobic photo-reforming of glycerol known as a by-product in biodiesel industry, towards production of chemicals and hydrogen. Solar-assisted reactions were performed by means of heterogeneous photocatalysis, in mild conditions such as atmospheric pressure, room temperature and water as a benign solvent. Titanium dioxide (lab-synthesized and commercial) was used as a photo-active catalyst, which surface was modified by introducing different metal (e.g. Au, Au-Cu, Pt) and metal oxide (e.g. NiO) nanoparticles. The prepared materials were characterized by XRD, DRS, BET, TEM, SEM, RAMAN and other techniques. The influence of the support, the size and type of the deposited metal and metal oxide nanoparticles on the photo-catalytic transformation of HMF and glycerol was evaluated. In the case of HMF, the influence of the base addition and the oxygen content on the reaction selectivity was also studied. The effect of the crystalline phase composition and morphology of TiO2 in the glycerol photo-reforming reaction was assessed as well. The surface of the synthesized TiO2 nano-powders was investigated by means of Surface Organometallic Chemistry (SOMC) approach. In particular, the surface was characterized by chemical titration and DRIFT techniques. Furthermore, the SOMC concept allowed preparing of well-dispersed Pt nanoparticles on the TiO2 surface. The photo-catalytic activity of this sample in the glycerol photo-reforming process was tested and compared to that of other Pt-containing catalysts prepared by conventional technics. In view of avoiding the agglomeration and sedimentation of suspended titania powders in water media, thick films of synthesized and commercial TiO2 were deposited on a conductive substrate using screen-printing technique. The prepared electrodes were characterized by profilometry, SEM, XRD, optical, electrochemical and photo-electrochemical methods.

Study on health status and remediation potential of Phragmites australis employed in an Emilia Romagna (IT) Constructed Wetland to assess zonal variability of the facility.

Phragmites australis (Cav.) Trin. ex Steud. is a hydrophyte particularly resistant to harsh conditions, e.g. drought, high salinity, contaminants, such as heavy metals and toxic molecules, and high nutrients concentrations. These resistances render the plant suitable for water depuration, where its particular metabolism is exploited to remove pollutants and excessive nutrients from the environment. In constructed wetlands, this principle is applied to phyto-purify wastewater with various origins, such as industrial, agricultural and household, with the aim to improve its quality to an extent which would render its reuse possible. In the framework of a pre-existing project of Department of Agricultural and Food Sciences (DiSTAl), this work integrates the knowledge and data relative to an Emilia Romagna (IT) constructed wetland plant, in order to expand the knowledge about this particular facility and of the system in general. By assaying antioxidants, both non- enzymatic and enzymatic, chlorophylls content and net photosynthetic rates, and by measuring the elemental composition of the specimens, the health status and the elemental uptake of the wetland plants sampled in different areas were investigated. The results were compared amongst the examined specimens with the aim to detect areas where there may be a higher stress due to a different wastewater composition, potentially varying along the constructed route. In addition, different parameters regarding the extraction and assay protocols were investigated, in order to optimise the procedure and to select the best conditions to perform the analyses, as well as to integrate information missing in literature or found as contradictory.

Study of the absorption of organic compounds on biopolymers

This work has been conducted in order to determine the solubility and diffusion coefficients of different aromatic substances in two different grades of polylactic acid (PLA), Amorphous (PDLLA) and Crystalline (PLLA); in particular the focus is on the following terpenes: Linalool, α-Pinene, β-Citronellol and L-Linalool. Moreover, further analyses have been carried out with the aim to verify if the use of neat crystalline PLA, (PLLA), a chiral substrate, may lead to an enantioenrichment of absorbed species in order to use it as membrane in enantioselective processes. The other possible applications of PLA, which has aroused interest in carry out the above-mentioned work, concerns its use in food packaging. Therefore, it is interesting and also very important, to evaluate the barrier properties of PLA, focusing in particular on the transport and absorption of terpenes, by the packaging and, hence, by the PLA. PLA films/slabs of one-millimeter thickness and with square shape, were prepared through the Injection Molding process. On the resulting PLA films heat pretreatment processes of normalizing were then performed to enhance the properties of the material. In order to evaluate solubility and diffusion coefficient of the different penetrating species, the absorption kinetics of various terpenes, in the two different types of PLA, were determined by gravimetric methods. Subsequently, the absorbed liquid was extracted with methanol (MeOH), non- solvent for PLA, and the extract analyzed by the use of High Performance Liquid Chromatography (HPLC), in order to evaluate its possible enantiomeric excess. Moreover, PLA films used were subjected to differential scanning calorimetry (DSC) which allowed to measure the glass transition temperature (Tg) and to determine the degree of crystallinity of the polymer (Xc).

Optimization and characterization of a wheat-based biocomposite for additive manufacturing

In recent years plastic is a key material, fundamental for a large variety of implications. But its large utilization has the direct consequence of the disposal of tons of wastes, that in the major amount cannot be recycled. To pose a solution to the issue of the increasing amount of plastics that are rapidly accumulating all over the world, it is necessary to switch to biodegradable materials. This dissertation is focused on a biodegradable and biobased plastic (polylactic acid, PLA), in order to set free the material from the market and issues of oil, but the PLA is very expensive. For this reason it was added a part of natural component derived from wastes (wheat middling), that acts as reinforcement and decreases the cost of the final material forming a biocomposite. Since their interaction is difficult, the purpose of this dissertation is to improve the affinity between the PLA and the wheat middling.

Study of the activity and enantioselectivity of alginate-based catalysts in Friedel-Crafts reactions

This thesis is part of a long-term project which aims to demonstrate for the first time that alginate gel beads can be used as chiral heterogeneous catalysts for enantioselective reactions. Alginate barium beads were prepared as previously optimized and applied to the Friedel-Crafts reaction between indoles and nitroalkenes. New substrates were tested, showing that the reaction can accommodate different nitroalkenes and indoles, affording the corresponding products with moderate yields and good enantioselectivities. However, aliphatic nitroalkenes cannot be used as they degrade under the catalytic reaction conditions. Preliminary study on the recyclability of the heterogeneous catalyst indicated a moderate stability of the catalyst, which can be used for few cycles with a slight erosion of enantioinducing power. Some directions for future improvements (storage and work-up solvent, use of ultrasonic bath) have been suggested.

Inkjet-printed poly(N-isopropylacrylamide)/graphene electrodes for selective electroanalytical sensing

The main research topic of the present master thesis consisted in the modification and electrochemical testing of inkjet printed graphene electrodes with a thin polymeric hydrogel layer made of cross-linked poly(N-isopropylacrylamide) (PNIPAAM) acting as a functional layer to fabricate selective sensors. The first experimental activities dealt with the synthesis of the polymeric hydrogel and the modification of the active surface of graphene sensors through photopolymerization. Simultaneous inkjet printing and photopolymerization of the hydrogel precursor inks onto graphene demonstrated to be the most effective and reproducible technique for the modification of the electrode with PNIPAAM. The electrochemical performance of the modified electrodes was tested through cyclic voltammetry. Voltammograms with standard redox couples with either positive, neutral or negative charges, suggested an electrostatic filtering effect by the hydrogel blocking negatively charged redox species in near neutral pH electrolyte solutions from reaching the electrode surface. PNIPAAM is a known thermo-responsive polymer, but the variation of temperature did not influence the filtering properties of the hydrogels for the redox couples studied. However, a variation of the filter capacity of the material was observed at pH 2 in which the PNIPAAM hydrogel, most likely in protonated form, became impermeable to positively charged redox species and permeable to negatively charged species. Finally, the filtering capacity of the electrodes modified with PNIPAAM was evaluated for the electrochemical determination of analytes in presence of negatively charge potential interferents, such as antioxidants like ascorbic acid. The outcome of the final experiments suggested the possibility to use the inkjet-printed PNIPAAM thin layer for electroanalytical applications as an electrostatic filter against interferents of opposite charges, typically present in complex matrices, such as food and beverages.