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Item Experimental investigation of system performance for combined desalination processes with membrane capacitive deionisation (MCDI)(Università della Calabria, 2021-10-31) Cañas Kurz, Edgardo E.; Critelli, Salvatore; Gabriele, Bartolo; Figoli, Alberto; Hoinkis, JanThe water supply in many coastal regions worldwide is affected by progressive salinization. Here, the use of desalination technologies is a viable solution for obtaining freshwater. In this thesis, two modular concepts for brackish water (BW) desalination by the use of membrane capacitive deionization (MCDI) and low-pressure reverse osmosis (LPRO) were developed and tested at laboratory and pilot-scales with two pilot plants installed in Vietnam. The two concepts were developed by using computer-based calculations (software: WAVE) and evaluated in a socioeconomic and environmental multi-criteria analysis. The first plant consisting of subsurface arsenic removal (SAR) as pre-treatment and MCDI for desalination was installed in Tra Vinh, in the Mekong Delta for the treatment of arseniccontaminated groundwater with a concentration of total dissolved solids (TDS) of 1.65 g/L. Results showed the feasibility of the modular concept for producing drinking water (TDS<0.45 g/L) with a specific energy consumption (SEC) of <3 kWh/m³. The relationship between feed salinity and specific ion removal of the MCDI was evaluated in real environment and compared with laboratory experiments. The use of renewable energies such as solar and wind for autonomous supply was proven feasible for these technologies. The second pilot plant was installed in a riverine estuary in the region of Cần Giờ, where no access to freshwater is available due to the progressive salinization of river water and groundwater. Here, river water showed TDS concentrations of up to 25 g/L. The combined system consisted of UF pre-treatment, LPRO and MCDI to produce drinking water and product water with TDS of <0.45 g/L and <1.5 g/L, respectively with a total SEC of 5.8 kWh/m³. Additionally, the performance of the LPRO was compared to seawater-RO (SWRO) in pilot trials, which showed a SEC of 5.5 kWh/m³. Although the SEC of single-stage SWRO was lower, the separate production of drinking and product water by LPRO+MCDI showed different advantages including a reduced SEC of 5.2 kWh/m³ for product water and additional 0.6 kWh/m³ for drinking water. Finally, an optimization of the LPRO+MCDI can be possible by increasing the desalination efficiency of the MCDI, increasing the efficiency of LPRO-pump and the MCDI power supply, and by aiming at feed water qualities with lower salinity.Item Theoretical Models for Membrane Capacitive Deionization for the design of Modular Desalination Processes(Università della Calabria, 2021-12-08) Hellriegel, Ulrich; Critelli, Salvatore; Gabriele, Bartolo; Figoli, Alberto; Hoinkis, JanDue to climate change, water scarcity will be exacerbated around the globe. To increase the water availability in regions at risk, water desalination plants can be a solution. Especially in rural areas, energy e cient technologies are needed so that an operation with renewable energy as photovoltaic modules can be feasible. Recent publications showed that the novel technology membrane capacitive deionization (MCDI) can achieve a lower speci c energy consumption (SEC) than reverse osmosis (RO), for brackish water desalination with salt concentrations below 2.5 g L-1. There is still a gap in research between laboratory operation and applied commercial scaled desalination, regarding experimental but also theoretical model studies. Therefore the latter is elaborated in the present PhD thesis. Hereby, existing models are reviewed, adapted and further developed to t to applied MCDI operation for drinking water production. Two dimensional nite element methods (FEM) modelling of ion transport, according to the Gouy-Chapman-Stern theory for electrical double layers (EDL) as well as computational uid dynamics (CFD) is combined with an adjusted semi-analytical modi ed Donnan (mD) model, with a constant excess chemical potential att = 2:33 kT, for the electrosorption of ions into porous active carbon electrodes. It predicts the e uent salt concentration time-dependently for di erent inputs of applied electrical currents Icell and voltages as well as inlet concentrations and volume ows. Applied MCDI operation was optimized for drinking water production with practical experiments, which support the evaluation of the theoretical ndings. The model ts to experimental data for Icell = 20 A, however the equations for the voltage over the electrodes need to be re-assessed so that the model ts for further input parameters. A CFD model of the water ow through large scaled MCDI modules (> 50 pairs of electodes) shows the need of constructing spacer thicknesses Sp small enough, to ensure equal retention times of the water between the electrodes in the module, which is important for stable diluate concentrations. Furthermore, an analytical calculation tool is developed, by adjusting the mD model and introducing an e ective salt adsorption capacity salt; , to predict the maximum e cient charging time tmax,ch, removal- and recovery rate as well as SEC values for optimized operation of applied MCDI processes. The model reaches an accuracy of 87% for the prediction of salt removal, 86% for tmax,ch and 75% for SEC values, compared with an experimental study and thus can be used to optimize the process design of applied MCDI desalination plants.Item Preparation of modified α-amino acids, useful building blocks for peptide sinthesis(2010-12-15) De Marco, Rosalia; Liguori, Angelo; Gabriele, BartoloItem Towards more sustainable organic processes : heterocyclizations in non-conventional solvents(2017-09-19) Maner, Asif S.; Carbone, Vincenzo; Gabriele, Bartolo; Mancuso, RaffaellaThis thesis reports the synthesis of important heterocyclic derivatives by iodocyclization, carbonylation and cycloisomerization reactions in Non-Conventionl solvents like deep eutectic solvents (DES) and Ionic Liquids (ILs). In chapter one general aspects of green and sustainable chemistry and introduction to eco-friendly green solvents such as water, DES, ScCO2 and ILs are described. Carbonylation processes, their advantages, types were described along with the application of transition metal catalysis in the carbonylation reactions with mechanistic approaches discussed. In chapter two, we describe a convenient and general method for the synthesis of substituted thiophenes through heterocyclodehydration and iodocyclization of readily available 1-mercapto-3-alkyn-2-ols in DES as the solvents. In chapter three we discuss a convenient carbonylative approach to 2-oxazolidinone derivatives carried out in an ionic liquid as the solvent (EmimEtSO4) is presented. It is based on the sequential concatenation of two catalytic cycles, both catalyzed by the same metal species (auto-tandem catalysis). In chapter four we present iodocyclization reactions to obtain iodinated isobenzofuranones and isochromenones by iodolactonization of 2-alkynyl benzoic acids in ionic liquids. In particular here we have developed divergent syntheses of (E)-3-(iodoalkylidene) isobenzofuran-1(3H)-ones and 4-iodo-1H-isochromen-1-ones by base-free Iodolactonization of 2-alkynylbenzoic acids in ionic liquids. In chapter five we report the cycloisomerization of readily available 2-alkynylbenzoic acids using an ionic liquid as the reaction medium in the presence of CuCl2 as a simple and inexpensive catalyst. Although in principle two different cyclization pathways can be followed, leading to either 5-exo-dig mode or 6-endo-dig mode, we have found that substrates bearing an aryl group on the triple bond or a terminal triple bond can be selectively converted into the isobenzofuranone derivatives, using N-ethyl-N-methylmorpholinium dicyanamide (Mor1,2N(CN)2) as the solvent. On the other hand, and in a complementary manner, substrates substituted with an alkyl or an alkenyl group on the triple bond selectively led to isochromenones when the reaction was carried out EmimEtSO4 and with excellent recyclability of the catalyst/ionic liquid system.Item Innovative fluorinated membranes for water and organic solvent treatment application(2017-09-19) Ursino, Claudia; Carbone, Vincenzo; Gabriele, Bartolo; Figoli, AlbertoThe aim of this thesis was to study the use of different types of fluoropolymer in order to prepare membranes for chemical and pharmaceutical applications. In fact, the potential use of fluoropolymeric membranes respect to other materials, at industrial levels, has several advantages such as high mechanical strength, high efficiency and stability. However, the unique properties of these materials such as excellent chemical and thermal strength make them extremely versatile but at the same time very difficult to process. As example, Ethylene-Chlorotrifluoroethylene (ECTFE) is insoluble in common organic solvents, and it can only be processed at high temperature, depending on the solvent used. In this work, three types of fluoropolymers have been studied, such as low-melting ECTFE (Halar®LMP-ECTFE), poly(vinylidene fluoride) (PVDF grade 1015) and perfluoropolyether (PFPEs) (Fluorolink®AD1700 and Fluorolink®MD700). Moreover, low-toxic solvents for humans and the environment have been appropriately selected and used for first time for solubilising the fluoropolymers of interest. -The Halar®LMP-ECTFE polymer was studied and characterized in terms of solubility parameters, compared with the standard Halar® ECTFE 901 polymer. In fact, this new grade of Halar® shows comparable properties with standard Halar® (hydrophobicity and mechanical properties), but lower crystallinity and lower melting point. Porous membranes and dense film were produced by thermally induced phase separation (TIPs). Two solvents, Diethyl Adipate (DEA) and Dibutyl Itaconate (DBI), never tested before, were selected. The chemical stability of the dense film was evaluated over time (192h) by swelling tests with aggressive organic solvents. Porous Halar®LMP-ECTFE membranes have been tested for organic solvents ultra- (UF) and nano-filtration (NF), such as methanol, ethanol and dimethylformamide. The results show that Halar®LMP ECTFE membranes are promising candidates to be used in separation processes under harsh conditions, such as chemicals production, purification and processing of food, nutraceuticals products and solvents recycling. - The influence of three different solvents in the membrane formation, using PVDF 1015 as polymer, was studied. Plasticizers from to Citroflex family, such as acetyl tributylcitrate (ATBC), acetyl triethylcitrate (ATEC) and triethylcitrate (TEC) have been selected and used. In particular ATEC and TEC as solvents, were used for the first time. Membranes were produced by thermally induced phase separation (TIPs) technique. The flat sheet membranes produced have been tested in microfiltration process (MF). These membranes can be used in several industrial applications such as sterilisation and clarification of pharmaceuticals or applied to separate contaminants from the water. - Perfluoropolyethers (PFPE) (Fluorolink®AD100 and Fluorolink®MD700) studied are new types of PFPE, UV cross-linkable. These PFPE photo-reticulated, have been used for coating commercial hydrophilic membrane, such as polyamide (PA) and polyethersulfone (PES) membranes. The aim of this work was to produce hydrophilic/hydrophobic coated membranes, keeping the morphology of the started membrane, unchanged. The study focused on morphological analysis, and on the influence of coating on the support membrane. The membranes produced, hydrophilic/hydrophobic, were characterized and the coating resistance was evaluated over time by direct contact with several chemical agents. The membranes were then tested, in membrane distillation process for direct contact (DCMD), using both deionized water and 0.6M saline. The results show that these coated membranes can be applied to desalination of seawater and wastewater treatment.Item Innovative UV-LED polymerised bicontinuous microemulsion coating for membranes with special emphasis on MBRs(2017-07-11) Schmidt, Slefan-André; Pantano, Pietro; Curcio, Efrem; Gabriele, Bartolo; Figoli, AlbertoThe main objective of this work is the preparation of polymerisable bicontinuous microemulsion (PBM) coatings applied onto commercial membranes for improving the anti-fouling properties and performance, in terms of water flux and foulants rejection. Microstructured and nanostructured materials obtained by PBM have been widely investigated in the course of the last 30 years. The interest in microemulsion lies mainly in the possibility of dissolving larger amounts of oil and water by using polymerisable and non-polymerisable surfactants. By polymerising the bicontinuous microemulsion it is possible to produce transparent porous polymeric solids [Gan et al. (1995), Gan and Chew (1997)]. This thesis represents the follow-up of the work done by Galiano et al. (2015) and Deowan et al. (2016). Galiano et al. (2015) developed the PBM composition that based on a non-polymerisable surfactant (DTAB) and another polymerisable surfactant (AUTEAB). In their work the PBM was polymerised by redox initiators leading to a process that is very difficult to up-scale for a commercial application. Critical issues were, the polymerisation time (at least 20 minutes), and the reproducibility of the coating. Therefore, it is the aim of this work to develop another polymerisation technique that increases the polymerisation speed and allows the easy reproduction of membranes with defined properties. The polymerisation by photoinitiators excited by UV-light represents a promising possibility for this requirement as it has the potential of decreasing the polymerisation time down to a few seconds. Several photoinitiators were selected for their compatibility with the PBM, and studied for their conversion rate efficiency (section 5.1.5). As there is a wide range of potential UV-light sources available, several technologies are studied for their coating performance (section 5.1.3). Subsequent to that, experiments were done in order to define the ideal photoinitiator type and concentration while polymerising onto glass plates. The coating onto commercial membranes is studied deeply for e.g. different casting knife thickness or ambient temperature (section 5.2.2 As the polymerisation under inert conditions is expected to increase the polymerisation speed, experiments are done, both under inert and non-inert conditions. The final membrane, coated under the optimum conditions, is further characterised for their permeability under different conditions like transmembrane pressure (TMP), model foulant experiments and a fixed volume flow (section 5.2.3). Further characterisation is done by contact angle, SEM, AFM (section 5.2.5 to 5.2.7). The prepared PBM membranes are foreseen to be finally applied for model textile dye wastewater treatment by Membrane BioReactor (MBR) technology. According to the previous results of Deowan et al. (2016) higher permeate quality through increased COD, TOC, dyestuffs removal efficiency and stronger anti-fouling properties are expected. Consequently, lower operation/maintenance costs due to reduced necessary aeration for scouring purposes and reduced membrane cleaning cycles as well as less membrane replacement are of special interest for commercial applications. In the previous work of Deowan et al. (2016) a lab scaled MBR with a single membrane housing was used. As of the biocenosis of the bacteria inside the reactor tank, a comparison of the membrane performance of the PBM and commercial membrane is difficult to achieve. Therefore an existing MBR system was redesigned to allow the simultaneous run of a commercial and a PBM coated membrane (section 4.1). As the revamp requires also additional sensors, the data acquisition needs to be adapted as well. To assure the proper function of the MBR the system was running for long term with two commercial membranes using a model textile wastewater (see 5.3.2). Finally the PBM coated membrane was compared with a commercial one for their performance in the MBR. Initial experiments for the water permeability are done as preparation for future work (see 5.3.3).Item Preparation of mixed matrix membranes for water treatment(2017-07-11) Grosso, Valentina; Panano, Pietro; Drioli, Enrico; Fontananova, Enrica; Di Profio, Gianluca; Curcio, Efrem; Gabriele, BartoloThe treatment of wastewater and its reuse is a very important topic in industrial processes. This because not only avoids drawing on natural resources, but also enables a significant reduction in the amount of wastewater discharged into the natural environment. Wastewater can also be used for various purposes where drinking water quality is not mandatory, including agricultural irrigation, the cleaning of industrial equipment, the watering of green spaces, and street maintenance, etc. In fact, the water reuse has become essential in all areas in the world that suffer from water shortages [1]. Different methods are used for wastewater treatment. These processes can be to divide in: primary, secondary and tertiary treatment. Primary treatment (screening, filtration, centrifugation, sedimentation, coagulation, gravity and flotation method) includes preliminary purification processes of a physical and chemical nature while secondary treatment deals with the biological treatment of wastewater. In tertiary treatment process wastewater is converted into good quality water that can be used for different types of purpose, i.e. drinking, industrial, medicinal etc. supplies [2]. The complexity of industrial processes, the variety of pollutants and the limitation of a single operation, has led to the need for more complex processes and especially to a combination of processes. Membranes technologies falls on the tertiary water treatment technologies and are actually the most effective separation processes and they are still in rapid development creating new prospects of their applications in clean technologies [3]. The utilization of membrane operations as hybrid systems, i.e. in combination with other conventional techniques or integrated with different membrane operations is considered the way forward for more rationale applications [4]. The possibilities of redesigning various industrial cycles by combining various membrane operations have been studies and in some case realized with a low environmental impact and a low energy consumption [5]. Different processes can be used in various steps of a hybrid system, depending from the size of the pollutants to be removed. Microfiltration (MF) and ultrafiltration (UF) membrane processes, can be used as pre-treatment, while nanofiltration (NF) and reverse osmosis (RO) can used in the final step of the integrated system to remove particles with smaller dimensions (Chapter 1) The membranes have different morphological characteristics that affect their performance. The study of all the conditions which modulate these characteristics is a crucial point in the choice of membranes to be used in the various separation processes. Therefore, it is important to investigate about new materials and new types of membranes, like as mixed matrix membrane (MMM). MMM is a heterogeneous membrane consisting of inorganic fillers embedded in a polymeric matrix and can be made into flat sheets and hollow-fiber. Nevertheless, the selection of membrane configuration is greatly dependent on the application and therefore the production of MMMs in useful configuration is undoubtedly a crucial point in membrane development [6]. Also, the selection of inorganic fillers depends of desired membrane performance and their use. More attention was focus on the interesting characteristic of carbonanotubes (CNTs) (chapter 2). CNTs themselves have remarkable electrical, thermal, and mechanical properties. These nanotubes have the structure of a rolled-up graphene sheet with smaller diameter. Multiwalled carbonanotube (MWCNTs) were used to prepare MMMs for wastewater treatment. Different compounds, as additives in the polymeric membranes were used in high percentage; in the case of MWCNTs was observed as a low amount can change the membrane morphologies, mechanical and transport properties. A crucial point was the choice of membrane materials. Two type, hydrophilic poly(imide) (PI) and hydrophobic poly(vinylidenfluoride) (PVDF) were choose for membrane materials to produce MMMs. Another important point in this study was the use of functionalized MWCNTs that provide a good dispersion in the casting solution first, and in the polymeric matrix after phase separation. The main limitation in the use of CNTs is their poor dispersion in the main solvents used for the preparation of membranes. The functionalization has been proven an efficient method to overcome this limitation improving the compatibility with the polymer matrix. The presence of polar groups on the carbon nanotubes can reduces their tendency to aggregate by van der Waals interactions, while forming hydrogen bonds and electron donor/acceptor interactions with the polymer. Low percentages of CNTs were used for the preparation of membranes. These percentages were sufficient to improve better performance to modified membranes. PI was select as polymeric materials because combine easy processability in the form of membranes, with a high chemical and thermal stability, over a wide range of operative conditions. Three different PI polymers were used to prepared porous asymmetric membrane by non-solvent induced phase separation (NIPS): a homopolymer (Matrimid) and two co-polymers (Lenzing P84 and Torlon). The effect of membrane preparation conditions on the membrane morphology and transport properties, were investigate. Moreover, mixed matrix based on co-polyimide P84 and functionalized multiwalled carbon nanotubes (oxidized and aminated MWCNTs) were prepared. The different polymeric membranes were compared in the rejection of organic dyes, as model of organic pollutant present in wastewater (chapter 3). To investigate about the influence of functional groups on the MWCNTs for their interaction with polymeric matrix, three different type of functionalized MWCNTs (oxidized, amined and aminated) were dispersed also in polymeric hydrophobic PVDF membranes. PVDF was selected as polymeric materials of its outstanding properties: excellent chemical resistance and hydrolytic stability; high mechanical strength and stability over a broad pH range; polymorphism (main crystalline phases are: α, β, γ, δ and ε) [7]. The aim was to tailor the interactions with the polymeric matrix in order to realize high performing composite film with improved performance. Bovine serum albumin (BSA) protein was select as compound to evaluate the membrane performance. In particular, the antifouling properties and the permeation flux of mixed matrix membranes, were evaluate as well as thermal and structural and mechanical properties (chapter 4).Item Synthesis of high value added molecules by catalytic and heterocyclization approaches(2018-05-11) Mancuso, Raffaella; Critelli, Salvatore; Gabriele, BartoloIn the present PhD thesis is reported the development of new sustainable catalytic processes for the production of high value added molecules starting from simple and readily available building blocks, under safer and low-intensive energy conditions, by iodocyclization, carbonylation and cycloisomerization reactions in non-conventionl solvents such as Deep Eutectic Solvents (DES) and Ionic Liquids (ILs). Catalytic processes, in which several different units can be assembled in one step in ordered sequence under the promoting action of a suitable catalyst, are destined to play a central role in current synthesis. Of particular importance is the development of novel catalytic processes for the reconversion of CO and CO2 into organic molecules. CO is an inexpensive and readily available C-1 source, and its incorporation into an organic substrate (carbonylation) is now widely recognized as a very important tool in synthesis. Nowadays, carbonylations are at the basis of important industrial technologies for the conversion of easily available feedstocks into useful products of our daily life, and find increasing application in organic synthesis for the production of fine chemicals. CO2 is another very attractive C-1 feedstock for organic synthesis. It is ubiquitously available, low toxic, and abundant. Since the industrial revolution, CO2 has been continuously released in huge amounts in the atmosphere from all combustion processes of organic carbon for the production of energy. Therefore, the efficient reconversion of CO2 (“spent” carbon) into high value added products (“working”-carbon; chemicals, fuels, materials) is one of the current most important strategic goals in chemical research, which will allow to make a step forward toward a more sustainable economy. Non-conventional solvents, such as polyethylene glycols, ionic liquids (ILs), Deep Eutectic Solvents, or supercritical CO2 are less toxic and more eco-friendly than traditional organic solvents. Their use in the processes studied in this thesis allowed an easier separation and purification of the products and, in the case of catalytic reactions, the recycling of the catalyst as well. The direct syntheses of ureas, oxamides, 2-oxazolidinones, and benzoxazolones by oxidative carbonylation of amines, β-amino alcohols, and 2-aminophenols allows obtaining high value added molecules, with a large number of important applications in several fields, starting from very simple building blocks. In chapter two is reported the possibility to carry out these transformations using the PdI2/KI catalytic system in an ionic liquid (IL), such as BmimBF4, as the solvent. The catalyst-solvent system can be recycled several times with only a slight loss of activity, while the product can be easily recovered by crystallization. In the some chapter the reactivity of 2-(2-alkynylphenoxy)anilines under PdI2/KI-catalyzed oxidative carbonylation conditions has been studied. 8-endo-dig cyclization preferentially occurred when the triple bond was terminal, leading to the formation of carbonylated β-lactam derivatives. These novel medium-sized heterocyclic compounds showed anti-tumor activity against both estrogen receptor-positive (MCF-7) and triple negative (MDA-MB-231) breast cancer cell lines. In chapter three is showed that the heterocyclodehydration and iodocyclization of readily available 1-mercapto-3-yn-2-ols has been performed in a deep eutectic solvent (DES), that is, ChCl/Gly, as a non-conventional green solvent. The DES/catalytic system could be easily recycled several times without appreciable loss of activity, after extraction of the thiophene product with hexane or Et2O. In chapter three the first example of a tandem thionation/S-cyclization process leading to benzo[c]thiophene-1(3H)-thione and 1H-isothiochromene-1-thione derivatives, starting from 2-alkynylbenzoic acids, is also reported. Depending on the nature of the substituent at the distal β carbon of the triple bond, either benzothiophenethiones or isothiochromenethiones were obtained selectively, in high to excellent yields. In chapter four a novel methodology to easily access imidazolidin-2-ones from propargylamines, primary amine and CO2 with guanidine bases as catalysts under solvent-free conditions is reported. Bicyclic guanidines, able to catalyze the formation of oxazolidinones from propargylamines and CO2, are presented for the first time as effective organocatalysts for the chemical fixation of CO2 into linear and cyclic ureas.Item Innovative composite membranes for advanced applications(2019-05-10) Grasso, Giuseppe; Critelli, Salvatore; Gabriele, BartoloPresented thesis work is mainly focused on coatings preparation, their potentiality and applications in membrane science: from water desalination to antibiofouling membranes, to gas separation. In fact, coating preparation represents an useful and versatile technique which allows a fine control of membrane properties and performance such as chemical or physical resistance, durability, etc. One of major drawbacks is represented by production costs, which can become important in scale-up operations. Therefore, although several type and methodologies for coating preparation are known and reported in literature, a lack of cheap, efficient and scale-up adaptable coating methods made their different preparation methods of particular interest. The results presented herein, concern the preparation of three different coating methods whose applications are briefly summarized below: Chapter 2: Development of PVDF-f-Graphene Thin Film Composite Membrane for Membrane Distillation Chapter 2 reports a novel method for TFC membrane fabrication, using graphene layer coated on chemically-functionalized PVDF. PVDF is hydrophobic polymer whose properties are well suited for those applications in which hydrophobicity is needed such as Membrane Distillation. In order to increase adhesion between PVDF and graphene, we co-polymerized PVDF with a suitable monomer bearing aromatic part, using a procedure which involves 2 steps reaction: introduction of double bonds on polymer backbone by basic treatment followed by its reaction with monomer through radical reaction. Membranes have been prepared using functionalized PVDF polymer (PVDF-f) and tested on Direct Contact Membrane Distillation (DCMD) apparatus at first. Subsequently tests were conducted using PVDF-f-Graphene composite membrane, using graphene synthetized using Chemical Vapor Deposition ( CVD) method. Created membranes were analyzed and their chemical, physical and morphological properties were investigated. Membranes made using PVDF-f polymer exhibited good flux and salt rejection (up to 99.9 %), whereas graphene association to PVDF-f membranes leads to lower water flux but higher rejection and durability (up to 99.99 %). In chapter 3 a simple and innovative synthetic strategy for Acryloyloxyalkiltriethyl ammonium salts surfactants (AATEABs) starting from cheap and easily available chemicals is discussed. Herein reported surfactants can be used as coating for membranes to whom they confer high anti biofouling properties. Synthetic procedure was first optimized in order to work avoiding prohibitive conditions such as Inert atmosphere or high temperature and then applied to the synthesis of surfactants bearing a different alkyl-chain length. Antibacterial activity evaluation, has been done performing several tests against Gram +\- and yeast strains; results confirmed that AATEABs bearing C11 (AUTEAB) and C12 (ADTEAB) alkyl chain possess highest activity which is remarkable high for ADTEAB. AATEABs may find applications as polymerizable coatings for watr-treatment membranes ( commercial or not) to be used in Pressure-Driven Membrane Processes or in any other membrane-based system in which antifouling properties may play an important role. Chapter 4: Thin Film Composite Membrane fabrication for gas separation: Defect control and bench-scale demonstration Fourth chapter of this thesis work, concerns the preparation of TFC membranes to be used for CO2/N2 separation, on the relationship between TFC membrane material and membrane properties and the role of the protective layer in determining the amount of defects, which is a crucial aspect for all the gas separation-related processes. We report a simple and efficient procedure which can also be applied to for defect controlling during scale-up process and which is not valid for CO2 separation membranes only. Results demonstrate a correlation between the properties of protective layer and separation performances: in particular, the possibility to apply a coating film on commercial membrane permits the creation of membranes in which the amount of defect is dramatically reduced. Another crucial aspect discussed in chapter 4 concerns the thickness of protective layer used for defect control: in fact, whereas the presence of protective layer plays an important role defect-free membrane creation process, its thickness impacts on separation operation. With our method, the preparation of membranes with very thin protective layer ( 0.1 μm or below) is possible.Item New palladium catalyzed carbonylation processes for the synthesis of molecules of applicative interest(2016-02-26) Ziccarelli, Ida; Mancuso, Raffaella; Gabriele, BartoloIn the present investigation we have developed new palladium-catalyzed carbonylation processes for the synthesis of molecules of applicative interest. In particular, isoindolinone and isobenzofuranimine derivatives have been synthetized starting from 2-alkynylbenzamides by a divergent PdI2-catalyzed multicomponent carbonylative approach, depending on the nature of the external nucleophile and reaction conditions. Thus, oxidative carbonylation of 2- ethynylbenzamides, bearing a terminal triple bond, carried out in the presence of a secondary amine as external nucleophile, selectively led to the formation of 3- [(dialkylcarbamoyl)methylene]isoindolin-1-ones. On the other hand, 3-[(alkoxycarbonyl)methylene]-isobenzofuran-1(3H)imines were selectively obtained when the oxidative carbonylation of 2-alkynylbenzamides, bearing a terminal or an internal triple bond, was carried out in the presence of an alcohol R'OH (such as methanol or ethanol) as the external nucleophile and HC(OR')3 as a dehydrating agent, necessary to avoid substrate hydrolysis. Isoindolinone derivatives were used as starting material to obtain the corresponding spiro-isoindolin isoxazolidines, able to work as inhibitors of the p53-MDM2 interaction: biological test showed that these compounds have antiproliferative activity on cancer cell lines of neuroblastoma, colorectal adenocarcinoma and hepatocarcinoma in the μM range. Isobenzofuranimine derivatives, instead, showed a strong phytotoxic effect on shoot and root systems of Arabidopsis thaliana, a weed which compete with crops for edaphic resources such as water and nutrients. Furo-furanone derivatives have been synthetized by PdI2-catalyzed oxidative carbonylation starting from 4-yn-1,3-diols, substrates bearing themselves nucleophilic groups in a suitable position to give a “double” intramolecular nucleophilic attack so as to obtain functionalized bicyclic molecules. Biological assay showed that these compounds are promising anticancer agents. Finally, part of this PhD was spent at Leibniz Institute for Catalysis in Rostock University in order to develop a new heterogeneous catalyst based on palladium via immobilization and pyrolysis on activated carbon. Palladium supported on N-doped carbon was applied to the alkoxycarbonylation of aryl iodides to benzoates, important feedstocks and key intermediates for pharmaceuticals.