964 resultados para yield per recruit
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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Maize demand for food, livestock feed, and biofuel is expected to increase substantially. The Western U.S. Corn Belt accounts for 23% of U.S. maize production, and irrigated maize accounts for 43 and 58% of maize land area and total production, respectively, in this region. The most sensitive parameters (yield potential [YP], water-limited yield potential [YP-W], yield gap between actual yield and YP, and resource-use efficiency) governing performance of maize systems in the region are lacking. A simulation model was used to quantify YP under irrigated and rainfed conditions based on weather data, soil properties, and crop management at 18 locations. In a separate study, 5-year soil water data measured in central Nebraska were used to analyze soil water recharge during the non-growing season because soil water content at sowing is a critical component of water supply available for summer crops. On-farm data, including yield, irrigation, and nitrogen (N) rate for 777 field-years, was used to quantify size of yield gaps and evaluate resource-use efficiency. Simulated average YP and YP-W were 14.4 and 8.3 Mg ha-1, respectively. Geospatial variation of YP was associated with solar radiation and temperature during post-anthesis phase while variation in water-limited yield was linked to the longitudinal variation in seasonal rainfall and evaporative demand. Analysis of soil water recharge indicates that 80% of variation in soil water content at sowing can be explained by precipitation during non-growing season and residual soil water at end of previous growing season. A linear relationship between YP-W and water supply (slope: 19.3 kg ha-1 mm-1; x-intercept: 100 mm) can be used as a benchmark to diagnose and improve farmer’s water productivity (WP; kg grain per unit of water supply). Evaluation of data from farmer’s fields provides proof-of-concept and helps identify management constraints to high levels of productivity and resource-use efficiency. On average, actual yields of irrigated maize systems were 11% below YP. WP and N-fertilizer use efficiency (NUE) were high despite application of large amounts of irrigation water and N fertilizer (14 kg grain mm-1 water supply and 71 kg grain kg-1 N fertilizer). While there is limited scope for substantial increases in actual average yields, WP and NUE can be further increased by: (1) switching surface to pivot systems, (2) using conservation instead of conventional tillage systems in soybean-maize rotations, (3) implementation of irrigation schedules based on crop water requirements, and (4) better N fertilizer management.
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This study evaluated the yield, components of production and oil content of two castor bean cultivars through drip irrigation with different water depths. The research was conducted in 2009 in an Oxisol clay in the experimental field in Dourados, Mato Grosso do Sul State. The experimental design was randomized blocks in factorial scheme with five water depths (0, 25, 50, 100 and 150% of evapotranspiration for drip irrigation) in two castor bean cultivars (IAC 2028 and IAC 80) with four replications. The irrigation schedule was predetermined up to two irrigations per week except on rainy days. The increase of irrigation provided significant increase in most components of production and crop yield without changing the oil content of seeds. The application of higher water depth increased yield by 80% in relation to the treatment that received no supplemental irrigation.
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Phenol and cresols represent a good example of primary chemical building blocks of which 2.8 million tons are currently produced in Europe each year. Currently, these primary phenolic building blocks are produced by refining processes from fossil hydrocarbons: 5% of the world-wide production comes from coal (which contains 0.2% of phenols) through the distillation of the tar residue after the production of coke, while 95% of current world production of phenol is produced by the distillation and cracking of crude oil. In nature phenolic compounds are present in terrestrial higher plants and ferns in several different chemical structures while they are essentially absent in lower organisms and in animals. Biomass (which contain 3-8% of phenols) represents a substantial source of secondary chemical building blocks presently underexploited. These phenolic derivatives are currently used in tens thousand of tons to produce high cost products such as food additives and flavours (i.e. vanillin), fine chemicals (i.e. non-steroidal anti-inflammatory drugs such as ibuprofen or flurbiprofen) and polymers (i.e. poly p-vinylphenol, a photosensitive polymer for electronic and optoelectronic applications). European agrifood waste represents a low cost abundant raw material (250 millions tons per year) which does not subtract land use and processing resources from necessary sustainable food production. The class of phenolic compounds is essentially constituted by simple phenols, phenolic acids, hydroxycinnamic acid derivatives, flavonoids and lignans. As in the case of coke production, the removal of the phenolic contents from biomass upgrades also the residual biomass. Focusing on the phenolic component of agrifood wastes, huge processing and marketing opportunities open since phenols are used as chemical intermediates for a large number of applications, ranging from pharmaceuticals, agricultural chemicals, food ingredients etc. Following this approach we developed a biorefining process to recover the phenolic fraction of wheat bran based on enzymatic commercial biocatalysts in completely water based process, and polymeric resins with the aim of substituting secondary chemical building blocks with the same compounds naturally present in biomass. We characterized several industrial enzymatic product for their ability to hydrolize the different molecular features that are present in wheat bran cell walls structures, focusing on the hydrolysis of polysaccharidic chains and phenolics cross links. This industrial biocatalysts were tested on wheat bran and the optimized process allowed to liquefy up to the 60 % of the treated matter. The enzymatic treatment was also able to solubilise up to the 30 % of the alkali extractable ferulic acid. An extraction process of the phenolic fraction of the hydrolyzed wheat bran based on an adsorbtion/desorption process on styrene-polyvinyl benzene weak cation-exchange resin Amberlite IRA 95 was developed. The efficiency of the resin was tested on different model system containing ferulic acid and the adsorption and desorption working parameters optimized for the crude enzymatic hydrolyzed wheat bran. The extraction process developed had an overall yield of the 82% and allowed to obtain concentrated extracts containing up to 3000 ppm of ferulic acid. The crude enzymatic hydrolyzed wheat bran and the concentrated extract were finally used as substrate in a bioconversion process of ferulic acid into vanillin through resting cells fermentation. The bioconversion process had a yields in vanillin of 60-70% within 5-6 hours of fermentation. Our findings are the first step on the way to demonstrating the economical feasibility for the recovery of biophenols from agrifood wastes through a whole crop approach in a sustainable biorefining process.
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The growth and the metabolism of Bifidobacterium adolescentis MB 239 fermenting GOS, lactose, galactose, and glucose were investigated. An unstructerd unsegregated model for growth of B. adolescentis MB 239 in batch cultures was developed and kinetic parameters were calculated with a Matlab algorithm. Galactose was the best carbon source; lactose and GOS led to lower growth rate and cellular yield, but glucose was the poorest carbon source. Lactate, acetate and ethanol yields allowed calculation of the carbon fluxes toward fermentation products. Similar distribution between 3- and 2-carbon products was observed on all the carbohydrates (45 and 55%, respectively), but ethanol production was higher on glucose than on GOS, lactose and galactose, in decreasing order. Based on the stoichiometry of the fructose 6-phosphate shunt and on the carbon distribution among the products, ATP yield was calculated on the different carbohydrates. ATP yield was the highest on galactose, while it was 5, 8, and 25% lower on lactose, GOS, and glucose, respectively. Therefore, a correspondance among ethanol production, low ATP yields, and low biomass production was established demonstrating that carbohydrate preferences may result from different sorting of carbon fluxes through the fermentative pathway. During GOS fermentation, stringent selectivity based on the degree of polymerization was exhibited, since lactose and the trisaccharide were first to be consumed, and a delay was observed until longer oligosaccharides were utilized. Throughout the growth on both lactose and GOS, galactose accumulated in the cultural broth, suggesting that β-(1-4) galactosides can be hydrolysed before they are taken up. The physiology of Bifidobacterium adolescentis MB 239 toward xylooligosaccharides (XOS) was also studied and our attention was focused on an extracellular glycosyl-hydrolase (β-Xylosidase) expressed by a culture of B. adolescentis grown on XOS as sole carbon source. The extracellular enzyme was purified from the the supernatant, which was dialyzed and concentrated by ultrafiltration. A two steps purification protocol was developed: the sample was loaded on a Mono-Q anion exchange chromatography and then, the active fractions were pooled and β-Xylosidase was purified by gel filtration chromatography on a Superdex-75. The enzyme was characterized in many aspects. β- Xylosidase was an homo-tetramer of 160 kDa as native molecular mass; it was a termostable enzyme with an optimum of temperature at 53 °C and an optimum of pH of 6.0. The kinetics parameter were calculated: km = 4.36 mM, Vmax = 0.93 mM/min. The substrate specificity with different di-, oligo- and polysaccharides was tested. The reactions were carried out overnight at pH 7 and at the optimum of temperature and the carbohydrates hydrolysis were analyzed by thin layer chromatography (TLC). Only glycosyl-hydrolase activities on XOS and on xylan were detected, whereas sucrose, lactose, cellobiose, maltose and raffinose were not hydrolyzed. It’s clearly shown that β-Xylosidase activity was higher than the Xylanase one. These studies on the carbohydrate preference of a strain of Bifidobacterium underlined the importance of the affinity between probiotics and prebiotics. On the basis of this concept, together with Barilla G&R f.lli SpA, we studied the possibility to develop a functional food containing a synbiotic. Three probiotic strains Lactobacillus plantarum BAR 10, Streptococcus thermophilus BAR 20, and Bifidobacterium lactis BAR 30 were studied to assess their suitability for utilization in synbiotic products on the basis of antioxidative activity, glutathione production, acid and bile tolerance, carbohydrates fermentation and viability in food matrices. Bile and human gastric juice resistance was tested in vitro to estimate the transit tolerance in the upper gastrointestinal tract. B. lactis and L. plantarum were more acid tolerant than S. thermophilus. All the strains resisted to bile. The growth kinetics on 13 prebiotic carbohydrates were determined. Galactooligosaccharides and fructo-oligosaccharides were successfully utilized by all the strains and could be considered the most appropriate prebiotics to be used in effective synbiotic formulations. The vitality of the three strains inoculated in different food matrices and maintained at room temperature was studied. The best survival of Lactobacillus plantarum BAR 10, Streptococcus thermophilus BAR 20, and Bifidobacterium lactis BAR 30 was found in food chocolate matrices. Then an in vivo clinical trial was carried out for 20 healthy volunteers. The increase in faecal bifidobacteria and lactobacilli populations and the efficacy of the pre-prototype was promising for the future develop of potential commercial products.
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Hospitals and health service providers are use to collect data about patient’s opinion to improve patient health status and communication with them and to upgrade the management and the organization of the health service provided. A lot of survey are carry out for this purpose and several questionnaire are built to measure patient satisfaction. In particular patient satisfaction is a way to describe and assess the level of hospital service from the patient’s point of view. It is a cognitive and an emotional response to the hospital experience. Methodologically patient satisfaction is defined as a multidimensional latent variable. To assess patient satisfaction Item Response Theory has greater advantages compared to Classical Test Theory. Rasch model is a one-parameter model which belongs to Item Response Theory. Rasch model yield objective measure of the construct that are independent of the set of people interviewed and of set of items used. Rasch estimates are continuous and can be useful to “calibrate” the scale of the latent trait. This research attempt to investigate the questionnaire currently adopted to measure patient satisfaction in an Italian hospital, completed by a large sample of 3390 patients. We verify the multidimensional nature of the variable, the properties of the instrument and the level of satisfaction in the hospital. Successively we used Rasch estimates to describe the most satisfied and the less satisfied patients.
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The digital electronic market development is founded on the continuous reduction of the transistors size, to reduce area, power, cost and increase the computational performance of integrated circuits. This trend, known as technology scaling, is approaching the nanometer size. The lithographic process in the manufacturing stage is increasing its uncertainty with the scaling down of the transistors size, resulting in a larger parameter variation in future technology generations. Furthermore, the exponential relationship between the leakage current and the threshold voltage, is limiting the threshold and supply voltages scaling, increasing the power density and creating local thermal issues, such as hot spots, thermal runaway and thermal cycles. In addiction, the introduction of new materials and the smaller devices dimension are reducing transistors robustness, that combined with high temperature and frequently thermal cycles, are speeding up wear out processes. Those effects are no longer addressable only at the process level. Consequently the deep sub-micron devices will require solutions which will imply several design levels, as system and logic, and new approaches called Design For Manufacturability (DFM) and Design For Reliability. The purpose of the above approaches is to bring in the early design stages the awareness of the device reliability and manufacturability, in order to introduce logic and system able to cope with the yield and reliability loss. The ITRS roadmap suggests the following research steps to integrate the design for manufacturability and reliability in the standard CAD automated design flow: i) The implementation of new analysis algorithms able to predict the system thermal behavior with the impact to the power and speed performances. ii) High level wear out models able to predict the mean time to failure of the system (MTTF). iii) Statistical performance analysis able to predict the impact of the process variation, both random and systematic. The new analysis tools have to be developed beside new logic and system strategies to cope with the future challenges, as for instance: i) Thermal management strategy that increase the reliability and life time of the devices acting to some tunable parameter,such as supply voltage or body bias. ii) Error detection logic able to interact with compensation techniques as Adaptive Supply Voltage ASV, Adaptive Body Bias ABB and error recovering, in order to increase yield and reliability. iii) architectures that are fundamentally resistant to variability, including locally asynchronous designs, redundancy, and error correcting signal encodings (ECC). The literature already features works addressing the prediction of the MTTF, papers focusing on thermal management in the general purpose chip, and publications on statistical performance analysis. In my Phd research activity, I investigated the need for thermal management in future embedded low-power Network On Chip (NoC) devices.I developed a thermal analysis library, that has been integrated in a NoC cycle accurate simulator and in a FPGA based NoC simulator. The results have shown that an accurate layout distribution can avoid the onset of hot-spot in a NoC chip. Furthermore the application of thermal management can reduce temperature and number of thermal cycles, increasing the systemreliability. Therefore the thesis advocates the need to integrate a thermal analysis in the first design stages for embedded NoC design. Later on, I focused my research in the development of statistical process variation analysis tool that is able to address both random and systematic variations. The tool was used to analyze the impact of self-timed asynchronous logic stages in an embedded microprocessor. As results we confirmed the capability of self-timed logic to increase the manufacturability and reliability. Furthermore we used the tool to investigate the suitability of low-swing techniques in the NoC system communication under process variations. In this case We discovered the superior robustness to systematic process variation of low-swing links, which shows a good response to compensation technique as ASV and ABB. Hence low-swing is a good alternative to the standard CMOS communication for power, speed, reliability and manufacturability. In summary my work proves the advantage of integrating a statistical process variation analysis tool in the first stages of the design flow.
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Adaptation and acclimation to different temperatures of obligate psychrophilic, facultative psychrophilic and mesophilic yeasts. Production of ω-3 and ω-6 polyunsaturated fatty acids by fermentative way. Obligate psychrophilic, facultative psychrophilic and mesophilic yeasts were cultured in a carbon rich medium at different temperatures to investigate if growth parameters, lipid accumulation and fatty acid composition were adaptive and/or acclimatory responses. Acclimation of facultative psychrophiles and mesophiles to lower temperature negatively affected their specific growth rate. Obligate psychrophiles exhibited the highest biomass yield (YX/S), followed by facultative psychrophiles, then by mesophiles. The growth temperature did not influence the YX/S of facultative psychrophiles and mesophiles. Acclimation to lower temperature caused the increase in lipid yield (YL/X) in mesophilic yeasts, but did not affect YL/X in facultative psychrophiles. Similar YL/X were found in both facultative and obligated psychrophiles, suggesting that lipid accumulation is not a distinctive character of adaptation to permanently cold environments. The extent of unsaturation of fatty acids was one major adaptive feature of the yeasts which colonize permanently cold ecosystems. Remarkable amounts of α-linolenic acid were found in obligate psychrophiles at the expenses of linoleic acid, whereas it was generally scarce or absent in all the others strains. Increased unsaturation of fatty acids was also an acclimatory response of mesophiles and facultative psychrophiles to lower temperature. It’s well known that omega-3 polyunsaturated fatty acids (PUFAs) display a variety of beneficial effects on various organ systems and diseases, therefore a process for the microbial production of omega-3 PUFAs would be of great interest. This work sought also to investigate if one of the better psychrophilic yeast, Rhodotorula glacialis DBVPG 4785, stimulated by acclamatory responses, produced omega-3 PUFAs. In fact, the adaptation of psychrophilic yeasts to cold niches is related to the production of higher amounts of lipids and to increased unsaturation degree of fatty acids, presumably to maintain membrane fluidity and functionality at low temperatures. Bioreactor fermentations of Rhodotorula glacialis DBVPG 4785 were carried out at 25, 20, 15, 10, 5, 0, and -3°C in a complex medium with high C:N ratio for 15 days. High biomass production was attained at all the temperatures with a similar biomass/glucose yield (YXS), between 0.40 and 0.45, but the specific growth rate of the strain decreased as the temperature diminished. The coefficients YL/X have been measured between a minimum of 0.50 to a maximum of 0.67, but it was not possible to show a clear effect of temperature. Similarly, the coefficient YL/S ranges from a minimum of 0.22 to a maximum of 0.28: again, it does not appear to be any significant changes due to temperature. Among omega-3 PUFAs, only α-linolenic acid (ALA, 18:3n-3) was found at temperatures below to 0°C, while, it’s remarkable, that the worthy arachidonic acid (C20:4,n-6), stearidonic acid (C20:4,n-3) C22:0 and docosahexaenoic acid (C22:6n-3) were produced only at the late exponential phase and the stationary phase of batch fermentations at 0 and -3°C. The docosahexaenoic acid (DHA) is a beneficial omega-3 PUFA that is usually found in fatty fish and fish oils. The results herein reported improve the knowledge about the responses which enable psychrophilic yeasts to cope with cold and may support exploitation of these strains as a new resource for biotechnological applications.
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Among various nanoparticles, noble metal nanoparticles have attracted considerable attention due to their optical, catalytic and conducting properties. This work has been focused on the development of an innovative method of synthesis for the preparation of metal nanosuspensions of Au, Ag, Cu, in order to achieve stable sols, showing suitable features to allow an industrial scale up of the processes. The research was developed in collaboration with a company interested in the large scale production of the studied nanosuspensions. In order to develop a commercial process, high solid concentration, long time colloidal stability and particle size control, are required. Two synthesis routes, differing by the used solvents, have been implemented: polyol based and water based synthesis. In order to achieve a process intensification the microwave heating has been applied. As a result, colloidal nanosuspensions with suitable dimensions, good optical properties, very high solid content and good stability, have been synthesized by simple and environmental friendly methods. Particularly, due to some interesting results an optimized synthesis process has been patented. Both water and polyol based synthesis, developed in the presence of a reducing agent and of a chelating polymer, allowed to obtain particle size-control and colloidal stability by tuning the different parameters. Furthermore, it has been verified that microwave device, due to its rapid and homogeneous heating, provides some advantages over conventional method. In order to optimize the final suspensions properties, for each synthesis it has been studied the effect of different parameters (temperature, time, precursors concentrations, etc) and throughout a specific optimization action a right control on nucleation and growth processes has been achieved. The achieved nanoparticles were confirmed by XRD analysis to be the desired metal phases, even at the lowest synthesis temperatures. The particles showed a diameter, measured by STEM and dynamic light scattering technique (DLS), ranging from 10 to 60 nm. Surface plasmon resonance (SPR) was monitored by UV-VIS spectroscopy confirming its dependence by nanoparticles size and shape. Moreover the reaction yield has been assessed by ICP analysis performed on the unreacted metal cations. Finally, thermal conductivity and antibacterial activity characterizations of copper and silver sols respectively are now ongoing in order to check their application as nanofluid in heat transfer processes and as antibacterial agent.
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In the recent years, consumers became more aware and sensible in respect to environment and food safety matters. They are more and more interested in organic agriculture and markets and tend to prefer ‘organic’ products more than their traditional counterparts. To increase the quality and reduce the cost of production in organic and low-input agriculture, the 6FP-European “QLIF” project investigated the use of natural products such as bio-inoculants. They are mostly composed by arbuscular mycorrhizal fungi and other microorganisms, so-called “plant probiotic” microorganisms (PPM), because they help keeping an high yield, even under abiotic and biotic stressful conditions. Italian laws (DLgs 217, 2006) have recently included them as “special fertilizers”. This thesis focuses on the use of special fertilizers when growing tomatoes with organic methods in open field conditions, and the effects they induce on yield, quality and microbial rhizospheric communities. The primary objective was to achieve a better understanding of how plant-probiotic micro-flora management could buffer future reduction of external inputs, while keeping tomato fruit yield, quality and system sustainability. We studied microbial rhizospheric communities with statistical, molecular and histological methods. This work have demonstrated that long-lasting introduction of inoculum positively affected micorrhizal colonization and resistance against pathogens. Instead repeated introduction of compost negatively affected tomato quality, likely because it destabilized the ripening process, leading to over-ripening and increasing the amount of not-marketable product. Instead. After two years without any significant difference, the third year extreme combinations of inoculum and compost inputs (low inoculum with high amounts of compost, or vice versa) increased mycorrhizal colonization. As a result, in order to reduce production costs, we recommend using only inoculum rather than compost. Secondly, this thesis analyses how mycorrhizal colonization varies in respect to different tomato cultivars and experimental field locations. We found statistically significant differences between locations and between arbuscular colonization patterns per variety. To confirm these histological findings, we started a set of molecular experiments. The thesis discusses preliminary results and recommends their continuation and refinement to gather the complete results.
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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.
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In durum wheat, two major QTL for grain yield (Qyld.idw-2B and Qyld.idw-3B) and related traits were identified in a recombinant population derived from Kofa and Svevo (Maccaferri et al. 2008). To further investigate the genetic and physiological basis of allelic variation for this important trait, the fine mapping of Qyld.idw-2B e Qyld.idw-3B was done during the PhD. In this regard, new molecular markers were added to increase the map resolution in the target interval. For Qyld.idw-2B region COS markers derived from the synteny between wheat and rice/ sorghum /brachypodiu genomes were screened. While for Qyld.idw-3B region SSR, ISBP and COS markers obtained from BAC end-sequences and BAC sequences generated during the construction of the 3B physical map (Paux et al., 2008) were screened. In the RIL population a final map resolution of 2,8 markers/cM for Qyld.idw-2B and 0,6 markers/cM for Qyld.idw-3B were obtained. Eighteen pairs of near-isogenic lines (NILs) for Qyld.idw-3B were obtained from F4:5 heterogeneous inbred families. In order to confirm the phenotypic effect of the QTL all pairs were evaluated in field trials (2010 and 2011) for all traits. Three pairs of NILs, with contrasted haplotypes at the target region, were crossed to produce a large F2 population (ca. 7,500 plants in total) that was screened for the identification of recombinants. A total of 233 homozygous F4:5 segmental isolines were obtained and the phenotypic and genotypic characterization of these materials were done. A fine mapping for Qyld.idw-3B was obtained and the QTL peak was identified in a interval of 0,4 cM. All markers were anchored to the Chinese Spring physical map of chr. 3B, which allowed us to identify the BAC Contigs spanning the QTL region and to assign the QTL peak to Contig 954. Sequencing of this contig has revealed the presence of 42 genes.
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La sostituzione di materie prime provenienti da risorse fossili con biomasse rinnovabili, utilizzando un processo a basso impatto ambientale, è una delle più importanti sfide della "Green Chemistry". Allo stesso tempo, la sintesi di resine epossidiche fornisce la chiave per la realizzazione di materiali ad alto valore aggiunto. Tuttavia, ad oggi, il 90% della produzione di resine epossidiche è basato sull'uso di bisfenolo A, che ha effetti di xenoestrogeno, ed epicloridrina, tossica e cancerogena. Su queste basi, è stata individuata una strategia sintetica per la sintesi di prepolimeri innovativi per resine epossidiche, che utilizza come substrato di reazione diidrossibenzeni di origine naturale ed evita l'uso di epicloridrina e altri reagenti tossici o pericolosi. La suddetta strategia sintetica è basata sulla sequenza: allilazione dei diidrossibenzeni - epossidazione dei doppi legami ottenuti. In questa procedura non vengono utilizzati drastiche condizioni di reazione e il solvente è acqua, con una catalisi di trasferimento di fase o, in aggiunte di acetonitrile, in un sistema bifasico. La resa complessiva dei due “step” dipende dalla posizione dei due ossidrili nei diidrossibenzeni. Il reagente che porta la resa massima è l’idrochinone (1,4 diidrossibenzene), che, come riportato in letteratura, permette la formazione di resine epossidiche con proprietà simili alle resine di epicloridrina e bisfenolo A. The substitution of raw materials from fossil fuels with renewable biomass using a low environmental impact process is one of the greatest challenges of the "Green Chemistry". At the same time, the synthesis of epoxy resins provides the key to the realization of high added value materials. However, 90% of the production of epoxy resins is based on the use of bisphenol A, a xenoestrogen, and epichlorohydrin, that is toxic and carcinogenic. On these bases, a synthetic strategy for the synthesis of innovative prepolymers of epoxy resins, that uses dihydroxybenzenes of natural origin as reaction substrates and avoids the use of epichlorohydrin and other toxic or dangerous reagents has been identified. The above synthetic strategy is based on the sequence: allylation of dihydroxybenzenes - epoxidation of the double bonds obtained. In this procedure, drastic reaction conditions are dismissed and the solvent used is water with a phase transfer catalysis or, in addition, acetonitrile in a biphasic system. The overall yield of the two steps depends on the position of the two hydroxyls of the dihydroxybenzenes. The reagent that leads to the highest yield is hydroquinone (1,4 dihydroxybenzene), which, as reported in literature, allows the formation of epoxy resins with similar properties to the resins from bisphenol A and epichlorohydrin.
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Microparticelle a base di complessi polielettrolitici di Chitosano/Pectina per il rilascio nasale di Tacrina cloridrato. Lo scopo di questo studio è stata la ricerca di nuove formulazioni solide per la somministrazione nasale di Tacrina cloridrato allo scopo di ridurre l’eccessivo effetto di primo passaggio epatico ed aumentarne la biodisponibilità a livello del Sistema Nervoso Centrale. La Tacrina è stata incapsulata in microparticelle mucoadesive a base di complessi elettrolitici di chitosano e pectina. Le microparticelle sono state preparate mediante due diversi approcci tecnologici (spray-drying e spray-drying/liofilizzazione) e analizzate in termini di caratteristiche dimensionali, morfologiche e chimico-fisiche. Nanoparticelle di Chitosano reticolate con Sodio Cromoglicato per il trattamento della rinite allergica. Il Sodio Cromoglicato è uno dei farmaci utilizzati per il trattamento della rinite allergica. Come noto, la clearance mucociliare provoca una rapida rimozione dei farmaci in soluzione dalla cavità nasale, aumentando così il numero di somministrazioni giornaliere e, di conseguenza, riducendo la compliance del paziente. Per ovviare a tale problema, si è pensato di includere il sodio cromoglicato in nanoparticelle di chitosano, un polimero capace di aderire alla mucosa nasale, prolungare il contatto della formulazione con il sito di applicazione e ridurre il numero di somministrazioni giornaliere. Le nanoparticelle ottenute sono state caratterizzate in termini di dimensioni, resa, efficienza di incapsulazione e caricamento del farmaco, potenziale zeta e caratteristiche mucoadesive. Analisi quantitativa di Budesonide amorfa tramite calorimetria a scansione differenziale. È stato sviluppato un nuovo metodo quantitativo allo stato solido basato sulla Calorimetria a Scansione Differenziale (DSC) in grado di quantificare in modo selettivo e accurato la quantità di Budesonide amorfa presente in una miscela solida. Durante lo sviluppo del metodo sono stati affrontati problemi relativi alla convalida di metodi analitici su campioni solidi quali la miscelazione di polveri solide per la preparazione di miscele standard e il calcolo della precisione.
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L’accoppiamento di diverse operazioni unitarie può in certi casi portare ad una cosiddetta “intensificazione di processo”, cioè ad un aumento sostanziale delle rese, dell’efficienza e della sostenibilità. Nel presente lavoro sono state pertanto analizzate le potenzialità di accoppiamento della fotocatalisi, il più studiato tra i “processi di ossidazione avanzata”, sia con alcuni processi a membrana per la sintesi verde di aromi sia con l’ozonizzazione per la depurazione di acque. È stato dimostrato che in entrambi i casi l’ottenimento di una significativa intensificazione di processo dipende in gran parte dai parametri operativi, in particolare dal rapporto, delta, tra la velocità caratteristica di fotocatalisi e quella del processo accoppiato. Nel caso della sintesi di aromi, in cui la fotocatalisi viene accoppiata con la pervaporazione o con la dialisi ricircolando al reattore il retentato dalla cella con la membrana. Il parametro delta dipende dalla velocità di reazione, dalle proprietà di trasporto delle membrane e naturalmente dal volume del rettore e dall’area della membrana. La reazione fotocatalitica produce l’aroma, ad esempio vanillina da acido ferulico, per ossidazione parziale e grazie al recupero del prodotto se ne evita l’ulteriore ossidazione aumentandone pertanto la resa. L’operare in apparati separati offre diversi vantaggi come la possibilità di variare senza vincoli il rapporto tra area della membrana e volume del reattore, ma impone di considerare anche il grado effettivo di accoppiamento dei processi. In questo caso, come evidenziato dal modello matematico, un sufficientemente elevato rapporto di ricircolo consente comunque di integrare efficacemente i processi. Nell’ozonizzazione fotocatalitica si hanno due importanti vantaggi: l’aumento della velocità di degradazione grazie alla sinergia tra i processi e la capacità di controllare la formazione di prodotti pericolosi. La sinergia viene massimizzata ad un valore ottimale di delta, mentre la formazione dei prodotti indesiderati viene controllata operando secondo le procedure che sono state individuate.