Studio della sintesi di alcol furfurilico da furfurale mediante catalisi basica eterogenea

La messa a punto di processi in grado di utilizzare le biomasse lignocellulosiche per la produzione di molecole piattaforma, utilizzabili per la sintesi di intermedi per la chimica fine, l’industria polimerica ed i combustibili, è attualmente un argomento di ricerca di grande interesse. Tra le molecole più studiate vi è la furfurale (FU), che si può ottenere mediante disidratazione dei monosaccaridi pentosi contenuti nei materiali lignocellulosici. Il prodotto di riduzione della furfurale, l’alcol furfurilico (FAL), è commercialmente interessante perché trova applicazione nell’industria polimerica e viene utilizzato come intermedio nella produzione di lisina, vitamina C, lubrificanti e agenti dispersanti. In letteratura sono riportati numerosi processi che permettono di ottenere questo prodotto, utilizzando la riduzione catalitica con H2 in pressione, che però presentano problemi di selettività, costo, sostenibilità e tossicità del catalizzatore utilizzato. La possibilità di effettuare la riduzione selettiva della furfurale senza fare ricorso all’idrogeno molecolare, utilizzando un processo di H-transfer e catalizzatori eterogenei a base di ossidi misti, risulta quindi di estremo interesse perché permette di eliminare i suddetti problemi. Lo scopo di questa tesi è stato quello di ottimizzare il processo, confrontando catalizzatori basici, quali MgO, CaO e SrO ottenuti tramite calcinazione a diverse temperature dei rispettivi precursori. In particolare, è stata valutata l’influenza che la temperatura di calcinazione, il tempo e la temperatura di reazione hanno sulla reattività e la stabilità dei sistemi catalitici sintetizzati. La caratterizzazione dei catalizzatori tramite diffrazione ai raggi X (XRD), analisi termiche (TGA, DTA) e misure di area superficiale con tecnica BET ha permesso di correlare le proprietà chimico-fisiche dei materiali con la loro attività catalitica.

Estimation of energy saving of commercial building by living wall and green facade in sub-tropical climate of Australia

This paper investigates energy saving potential of commercial building by living wall and green façade system using Envelope Thermal Transfer Value (ETTV) equation in Sub-tropical climate of Australia. Energy saving of four commercial buildings was quantified by applying living wall and green façade system to the west facing wall. A field experimental facility, from which temperature data of living wall system was collected, was used to quantify wall temperatures and heat gain under controlled conditions. The experimental parameters were accumulated with extensive data of existing commercial building to quantify energy saving. Based on temperature data of living wall system comprised of Australian native plants, equivalent temperature of living wall system has been computed. Then, shading coefficient of plants in green façade system has been included in mathematical equation and in graphical analysis. To minimize the air-conditioned load of commercial building, therefore to minimize the heat gain of commercial building, an analysis of building heat gain reduction by living wall and green façade system has been performed. Overall, cooling energy performance of commercial building before and after living wall and green façade system application has been examined. The quantified energy saving showed that only living wall system on opaque part of west facing wall can save 8-13 % of cooling energy consumption where as only green façade system on opaque part of west facing wall can save 9.5-18% cooling energy consumption of commercial building. Again, green façade system on fenestration system on west facing wall can save 28-35 % of cooling energy consumption where as combination of both living wall on opaque part of west facing wall and green façade on fenestration system on west facing wall can save 35-40% cooling energy consumption of commercial building in sub-tropical climate of Australia.

Investigation of cooling energy performance of commercial building in sub-tropical climate through the application of green roof and living wall

This paper investigates cooling energy performance of commercial building before and after green roof and living wall application based on integrated building heat gain model developed from Overall Thermal Transfer Value (OTTV) of building wall and steady state heat transfer process of roof in sub-tropical climate. Using the modelled equation and eQUEST energy simulation tool, commercial building envelope parameters and relevant heat gain parameters have been accumulated to analyse the heat gain and cooling energy consumption of commercial building. Real life commercial building envelope and air-conditioned load data for the sub-tropical climate zone have been collected and compared with the modelled analysis. Relevant temperature data required for living wall and green roof analysis have been collected from experimental setup comprised of both green roof and west facing living wall. Then, Commercial building heat flux and cooling energy performance before and after green roof and living wall application have been scrutinized.

The composition of sugarcane juices dervied from burnt cane and whole green cane crop

There has been substantial interest within the Australian sugar industry in product diversification as a means to reduce its exposure to fluctuating raw sugar prices and in order to increase its commercial viability. In particular, the industry is looking at fibrous residues from sugarcane harvesting (trash) and from sugarcane milling (bagasse) for cogeneration and the production of biocommodities, as these are complementary to the core process of sugar production. A means of producing surplus residue (biomass) is to process whole sugarcane crop. In this paper, the composition of different juices derived from different harvesting methods, viz. burnt cane with all trash extracted (BE), green cane with half of the trash extracted (GE), and green cane (whole sugarcane crop) with trash unextracted (GU), were investigated and the results and comparison presented. The determination of electrical conductivity, inorganic composition, and organic acids indicate that both GU and GE cane juice contain a higher proportion of soluble inorganic ions and ionisable organic acids, compared to BE cane juice. It is important to note that there are considerably higher levels of Na ions and citric acid, but relatively low P levels in the GU samples. A higher level of reducing sugars was analysed in the GU samples than the BE samples due to the higher proportion of impurities found naturally in sugarcane tops and leaves. The purity of the first expressed juice (FEJ) of GU cane was on average higher than that of FEJ of BE cane. Results also show that GU juices appear to contain higher levels of proteins and polysaccharides, with no significant difference in starch levels.

R&D investment in green building initiatives in Western Australia

This paper reports on a current case study of green building initiatives implemented by the Western Australian government in the past decade. The intent is to provide a qualitative understanding of past R&D investments in the Australian built environment. The case method was selected to illustrate three sector-based investments, one of which is reported on here. The conceptual framework underpinning interview design and data analysis uses dynamic capability, absorptive capacity and open innovation theories to better understand the organisational environment in which these initiatives were implemented. Data has been thematically coded to criteria identified from the literature to illustrate organisational characteristics which may have contributed to dissemination and impact. The results will be combined with two further case studies (construction safety and digital modelling), to inform this research. This industry supported project will conclude by developing policy guidelines for future R&D investment in the built environment.

Post occupancy evaluations relating to discomfort glare : a study of green buildings in Brisbane

Glare indices have yet to be extensively tested in daylit open plan offices, as such there is no effective method to predict discomfort glare within these spaces. This study into discomfort glare in open plan green buildings targeted full-time employees, working under their everyday lighting conditions. Three green buildings in Brisbane were used for data collection, two were Green Star accredited and the other contained innovative daylighting strategies. Data were collected on full-time employees, mostly aged between 30 and 50 years, who broadly reflect the demographics of the wider working population in Australia. It was discovered 36 of the 64 respondents experienced discomfort from both electric and daylight sources at their workspace. The study used a specially tailored post-occupancy evaluation (POE) survey to help assess discomfort glare. Luminance maps extracted from High Dynamic Range (HDR) images were used to capture the luminous environment of the occupants. These were analysed using participant data and the program Evalglare. The physical results indicated no correlation with other developed glare metrics for daylight within these open plan green buildings, including the recently developed Daylight Glare Probability (DGP) Index. The strong influence of vertical illuminance, Ev in the DGP precludes the mostly contrast-based glare from windows observed in this investigation from forming a significant part of this index. Furthermore, critical assessment of the survey techniques used are considered. These will provide insight for further research into discomfort glare in the endeavour to fully develop a suitable glare metric.

Effect of coffee combining green coffee bean constituents with typical roasting products on the Nrf2/ARE pathway in vitro and in vivo

This study investigated Nrf2-activating properties of a coffee blend combining raw coffee bean constituents with 5-O-caffeoylquinic acid (CGA) as a lead component with typical roasting products such as N-methylpyridinium (NMP). In cell culture (HT29) the respective coffee extract (CN-CE) increased nuclear Nrf2 translocation and enhanced the transcription of ARE-dependent genes as exemplified for NAD(P)H:quinone oxidoreductase and glutathione-S-transferase (GST)A1, reflected in the protein level by an increase in GST enzyme activity. In a pilot human intervention study (29 healthy volunteers), daily consumption of 750 mL of CN-coffee for 4 weeks increased Nrf2 transcription in peripheral blood lymphocytes on average. However, the transcriptional response pattern of Nrf2/ARE-dependent genes showed substantial interindividual variations. The presence of SNPs in the Nrf2-promoter, reported recently, as well as the detection of GSTT1*0 (null) genotypes in the study collective strengthens the hypothesis that coffee acts as a modulator of Nrf2-dependent gene response in humans, but genetic polymorphisms play an important role in the individual response pattern.

Discomfort glare in open plan green buildings

This study presents the largest-known, investigation on discomfort glare with 493 surveys collected from five green buildings in Brisbane, Australia. The study was conducted on full-time employees, working under their everyday lighting conditions, all of whom had no affiliation with the research institution. The survey consisted of a specially tailored questionnaire to assess potential factors relating to discomfort glare. Luminance maps extracted from high dynamic range (HDR) images were used to capture the luminous environment of the occupants. Occupants who experienced glare on their monitor and/or electric glare were excluded from analysis leaving 419 available surveys. Occupants were more sensitive to glare than any of the tested indices accounted for. A new index, the UGP was developed to take into account the scope of results in the investigation. The index is based on a linear transformation of the UGR to calculate a probability of disturbed persons. However all glare indices had some correlation to discomfort, and statistically there was no difference between the DGI, UGR and CGI. The UGP broadly reflects the demographics of the working population in Australia and the new index is applicable to open plan green buildings.

Tuning the surface structure of nitrogen-doped TiO2Nanofibres : an effective method to rnhance photocatalytic activities of visible-light-driven green synthesis and degradation

Nitrogen-doped TiO2 nanofibres of anatase and TiO2(B) phases were synthesised by a reaction between titanate nanofibres of a layered structure and gaseous NH3 at 400–700 °C, following a different mechanism than that for the direct nitrogen doping from TiO2. The surface of the N-doped TiO2 nanofibres can be tuned by facial calcination in air to remove the surface-bonded N species, whereas the core remains N doped. N-Doped TiO2 nanofibres, only after calcination in air, became effective photocatalysts for the decomposition of sulforhodamine B under visible-light irradiation. The surface-oxidised surface layer was proven to be very effective for organic molecule adsorption, and the activation of oxygen molecules, whereas the remaining N-doped interior of the fibres strongly absorbed visible light, resulting in the generation of electrons and holes. The N-doped nanofibres were also used as supports of gold nanoparticle (Au NP) photocatalysts for visible-light-driven hydroamination of phenylacetylene with aniline. Phenylacetylene was activated on the N-doped surface of the nanofibres and aniline on the Au NPs. The Au NPs adsorbed on N-doped TiO2(B) nanofibres exhibited much better conversion (80 % of phenylacetylene) than when adsorbed on undoped fibres (46 %) at 40 °C and 95 % of the product is the desired imine. The surface N species can prevent the adsorption of O2 that is unfavourable for the hydroamination reaction, and thus, improve the photocatalytic activity. Removal of the surface N species resulted in a sharp decrease of the photocatalytic activity. These photocatalysts are feasible for practical applications, because they can be easily dispersed into solution and separated from a liquid by filtration, sedimentation or centrifugation due to their fibril morphology.

The application of luminance mapping to discomfort glare : a modified glare index for green buildings

Unfortunately, there is no reliable method to adequately quantify discomfort glare. One of the world's largest investigations on discomfort glare was conducted in five Green Star office buildings in Brisbane. Luminance mapping via high dynamic range images and Post Occupancy Evaluation surveys were used in the data collection. A new glare index, termed the Unified Glare Probability, was developed to predict discomfort glare within these types of office buildings.

Critical-point Properties of Liquids and the Born-Green Theory

Recent work of Jones et al. giving the long-range behaviour of the pair correlation function is used to confirm that the critical ratio Pc/nckBTc = 1/2 in the Born-Green theory. This deviates from experimental results on simple insulating liquids by more than the predictions of the van der Waals equation of state. A brief discussion of conditions for thermodynamic consistency, which the Born-Green theory violates, is then given. Finally, the approach of the Ornstein-Zernike correlation function to its critical point behaviour is discussed within the Born-Green theory.

Metal nanoparticle photocatalysts: Emerging processes for green organic synthesis

Metal nanoparticle photocatalysts have attracted recent interest due to their strong absorption of visible and ultraviolet light. The energy absorbed by the metal conduction electrons and the intense electric fields in close proximity, created by the localized surface plasmon resonance effect, makes the crucial contribution of activating the molecules on the metal nanoparticles which facilitates chemical transformation. There are now many examples of successful reactions catalyzed by supported nanoparticles of pure metals and of metal alloys driven by light at ambient or moderate temperatures. These examples demonstrate these materials are a novel group of efficient photocatalysts for converting solar energy to chemical energy and that the mechanisms are distinct from those of semiconductor photocatalysts. We present here an overview of recent research on direct photocatalysis of supported metal nanoparticles for organic synthesis under light irradiation and discuss the significant reaction mechanisms that occur through light irradiation.

Role of the triplet state in the green emission peak of polyfluorene films: A time evolution study

The blue emission of ethyl-hexyl substituted polyfluorene (PF2/6) films is accompanied by a low energy green emission peak around 500 nm in inert atmosphere. The intensity of this 500 nm peak is large in electroluminescence (EL) compared to photoluminescence (PL)measurements. Furthermore, the green emission intensity reduces dramatically in the presence of molecular oxygen. To understand this, we have modeled various nonradiative processes by time dependent quantum many body methods. These are (i) intersystem crossing to study conversion of excited singlets to triplets leading to a phosphorescence emission, (ii) electron-hole recombination (e-hR) process in the presence of a paramagnetic impurity to follow the yield of triplets in a polyene system doped with paramagnetic metal atom, and (iii) quenching of excited triplet states in the presence of oxygen molecules to understand the low intensity of EL emission in ambient atmosphere, when compared with that in nitrogen atmosphere. We have employed the Pariser-Parr-Pople Hamiltonian to model the molecules and have invoked electron-electron repulsions beyond zero differential approximation while treating interactions between the organic molecule and the rest of the system. Our time evolution methods show that there is a large cross section for triplet formation in the e-hR process in the presence of paramagnetic impurity with degenerate orbitals. The triplet yield through e-hR process far exceeds that in the intersystem crossing pathway, clearly pointing to the large intensity of the 500 nm peak in EL compared to PL measurements. We have also modeled the triplet quenching process by a paramagnetic oxygen molecule which shows a sizable quenching cross section especially for systems with large sizes. These studies show that the most probable origin of the experimentally observed low energy EL emission is the triplets.

Towards a green synthesis of isoquinoline: Beckmann rearrangement of E,-cinnamaldoxime over H-zeolites

Isoquinoline was prepared through the Beckmann rearrangement of cinnamaldoxime over different H-zeolites, K-10 montmorillonite clay, amorphous SiO2–Al2O3 and γ-alumina under well-optimized conditions of temperature, weight hourly space velocity and catalyst loading. Cinnamaldoxime under ambient reaction conditions over the catalysts underwent migration of the anti-styryl moiety to electron deficient nitrogen (Beckmann rearrangement) followed by an intramolecular cyclization to yield isoquinoline. Cinnamo-nitrile (dehydration product) and cinnamaldehyde were formed as by-products. Isoquinoline formation was high on zeolite catalysts (ca. >86.5%) and mordenite (ca. 92.3%) was the most efficient in the series. Catalysts were susceptible for deactivation and the decrease in the percentage conversion of oxime with time is associated with a corresponding increase in the acid hydrolysis producing salicylaldehyde at later stages of the reaction. However, these catalysts retain activity considerably and can be recycled without loss of activity and change of product distribution.