Microwave-Assisted Protocol for Green Functionalization of Thiophenes With a Pd/β-Cyclodextrin Cross-Linked Nanocatalyst

Microwaves (MW) are often the most efficient, in terms of heat exchange and conversion rate, of all the energy sources used to promote chemical reactions thanks to fast volumetric dielectric heating, and metal-catalyzed synthetic reactions under heterogeneous conditions are an eloquent example. We herein report a MW-assisted green protocol for the C-H arylation of thiophenes with substituted aryl halides. This sustainable protocol carried out in γ-valerolactone (GVL) is catalyzed by Pd nanoparticles embedded in cross-linked β-cyclodextrin. In view of the excellent results achieved with activated substrates, the one-pot synthesis of a 4(3H)-quinazolinone derivative has been accomplished. A pressure-resistant MW reactor, equipped with multiple gas inlets, was used for sequential (i) C-H arylation, (ii) reduction, and (iii) carbonylation in the presence of the same catalyst, but under different gas atmospheres. The robust heterogeneous Pd catalyst showed limited metal leaching in GVL, making this an efficient MW-assisted process with high atom economy

From seaweeds to cosmeceutics: A multidisciplinar approach

Macroalgae are widespread on the coasts of all the globe and lead to a negative ecological impact, requiring expensive remediations. Therefore, the valorization of invasive seaweed as a renewable source of bioactive products could represent a valid solution. In this context, three algal biomasses, belonging to brown, green, and red families (Sargassum muticum, Ulva lactuca, Solieria filiformis), collected in the venetian Laguna, were investigated as a source of active compounds for the formulation of cosmeceutics. Microwave (MW) and ultrasound (US) were applied to enhance the algae extraction by means of a hydroalcoholic solution. According to total phenolic content (TPC) evaluation, MW demonstrated the best performing outcomes, resulting in 19.77, 22.02, and 16.94 mgGAE/gExtr (30 min at 90◦C) for brown, green, and red algae, respectively. Antioxidant activity was tested as well, showing comparable trends (49.19, 26.24, and 3.02 mmolTrolox eq./gExtr for brown, green, and red algae, respectively). Due to natural algae predisposition to absorb contaminants, the metal content analysis helped to screen the applicability of these extracts, identifying Ulva lactuca as the most suitable source of antioxidants for cosmetic formulations. This MW extract was then adopted to formulate two different preparations, namely a gel and an emulsion. Thermal and mechanical tests confirmed the stability of each formulation, together with neutral organoleptic characteristics. Finally, the actives release was investigated by means of a tape stripping essay, showing an efficient controlled release for gel formulation, even after 7 h of test. The produced cosmeceutics merged non-conventional extraction technologies with formulation expertise, offering a valuable alternative to solve the macroalgae disposal issue

Sustainable isosorbide production by a neat one-pot MW-assisted catalytic glucose conversion

In the context of exploitation of new biomass-derived platform chemicals, isosorbide (1,4:3,6-dianhydro-D-sorbitol), obtained by the two-fold dehydration of sorbitol, is gaining increasing interest in several potential industrial applications. Seeking for more sustainable, efficient, and economically competitive green processes, the use of heterogeneous catalysts under microwave (MW) irradiation has been adopted for the development of a neat one-pot process from glucose. MW-assisted catalytic processes have shown the potential to reduce the reaction time and improve the selectivity, due to the interaction of MW with the reaction medium through the production of hot spots on the catalyst surface. Ru/C, Ru/Al2O3 and Ru/TiO2 were tested for glucose hydrogenation to sorbitol, while the dehydration step was favored by the addition of beta Zeolites (360:1 SiO2:Al2O3) allowing high isosorbide selectivity (>85 %). An extended structural and morphological characterization before and after the catalytic tests allowed to establish structure-activity relationships. Yields up to 47.1 % have been obtained directly from glucose in 1.5 h, achieving a considerable reduction of reaction time without the use of a solvent. thus paving the way for further investigations on biomass conversion into value-added products. With this aim, direct isosorbide production from milled cellulose was investigated. While the isosorbide yields still need to be improved, the dual role of formic acid both as acid catalyst for cellulose hydrolysis and H-donor for the reduction step was promisingly clarified

Cross-linked cyclodextrins bimetallic nanocatalysts: Applications in microwave-assisted reductive aminations

The optimization of sustainable protocols for reductive amination has been a lingering challenge in green synthesis. In this context, a comparative study of different metal-loaded cross-linked cyclodextrins (CDs) were examined for the microwave (MW)-assisted reductive amination of aldehydes and ketones using either H2 or formic acid as a hydrogen source. The Pd/Cu heterogeneous nanocatalyst based on Pd (II) and Cu (I) salts embedded in a β-CD network was the most efficient in terms of yield and selectivity attained. In addition, the polymeric cross-linking avoided metal leaching, thus enhancing the process sustainability; good yields were realized using benzylamine under H2. These interesting findings were then applied to the MW-assisted one-pot synthesis of secondary amines via a tandem reductive amination of benzaldehyde with nitroaromatics under H2 pressure. The formation of a CuxPdy alloy under reaction conditions was discerned, and a synergic effect due to the cooperation between Cu and Pd has been hypothesized. During the reaction, the system worked as a bifunctional nanocatalyst wherein the Pd sites facilitate the reduction of nitro compounds, while the Cu species promote the subsequent imine hydrogenation affording structurally diverse secondary amines with high yields

XPS characterization of (copper-based) coloured stains formed on limestone surfaces of outdoor Roman monuments

Limestone basements holding bronzes or other copper alloys artefacts such as sculptures, decorations and dedicatory inscriptions are frequently met both in modern and ancient monuments. In outdoor conditions, such a combination implies the corrosion products of the copper based alloy, directly exposed to rainwater, will be drained off and migrate through the porous surfaces, forming stains of different colours and intensities, finally causing the limestone structures to deteriorate

Overview of ASDEX Upgrade results

Recent results from the ASDEX Upgrade experimental campaigns 2001 and 2002 are presented. An improved understanding of energy and particle transport emerges in terms of a 'critical gradient' model for the temperature gradients. Coupling this to particle diffusion explains most of the observed behaviour of the density profiles, in particular, the finding that strong central heating reduces the tendency for density profile peaking. Internal transport barriers (ITBs) with electron and ion temperatures in excess of 20 keV (but not simultaneously) have been achieved. By shaping the plasma, a regime with small type II edge localized modes (ELMs) has been established. Here, the maximum power deposited on the target plates was greatly reduced at constant average power. Also, an increase of the ELM frequency by injection of shallow pellets was demonstrated. ELM free operation is possible in the quiescent H-mode regime previously found in DIII-D which has also been established on ASDEX Upgrade. Regarding stability, a regime with benign neoclassical tearing modes (NTMs) was found. During electron cyclotron current drive (ECCD) stabilization of NTMs, βN could be increased well above the usual onset level without a reappearance of the NTM. Electron cyclotron resonance heating and ECCD have also been used to control the sawtooth repetition frequency at a moderate fraction of the total heating power. The inner wall of the ASDEX Upgrade vessel has increasingly been covered with tungsten without causing detrimental effects on the plasma performance. Regarding scenario integration, a scenario with a large fraction of noninductively driven current (≥50%), but without ITB has been established. It combines improved confinement (τE/τITER98 ≈ 1.2) and stability (βN ≤ 3.5) at high Greenwald fraction (ne/nGW ≈ 0.85) in steady state and with type II ELMy edge and would offer the possibility for long pulses with high fusion power at reduced current in ITER

Where are the returns to lifelong learning?

Participation in formal education during adulthood (ages 25 to 54) is a key part of lifelong learning. Employing unique longitudinal data for Australia, we highlight the prevalence of such study, the varied reasons for undertaking it (consumption, career development, job and home disruption), and investigate whether it is socially valuable. Our more detailed estimates of the labour market return to adult education (wage rates, employment, hours of work and occupational status) confirm previous studies that generally found such returns to be small and isolated. We contribute to this literature by also estimating the effect of adult education on job satisfaction and satisfaction with employment opportunities. Increases in satisfaction help rationalise the education enrolment decisions of these adults