Dye‐Doped Polyhedral Oligomeric Silsesquioxane (POSS)‐Modified Polymeric Matrices for Highly Efficient and Photostable Solid‐State Lasers

Here, the design, synthesis, and characterization of laser nanomaterials based on dye‐doped methyl methacrylate (MMA) crosslinked with octa(propyl‐methacrylate) polyhedral oligomeric silsesquioxane (8MMAPOSS) is reported in relation to their composition and structure. The influence of the silicon content on the laser action of the dye pyrromethene 567 (PM567) is analyzed in a systematic way by increasing the weight proportion of POSS from 1 to 50%. The influence of the inorganic network structure is studied by replacing the 8MMAPOSS comonomer by both the monofunctionalized heptaisobutyl‐methacryl‐POSS (1MMAPOSS), which defines the nanostructured linear network with the POSS cages appearing as pendant groups of the polymeric chains, and also by a new 8‐hydrogenated POSS incorporated as additive to the polymeric matrices. The new materials exhibit enhanced thermal, optical, and mechanical properties with respect to the pure organic polymers. The organization of the molecular units in these nanomaterials is studied through a structural analysis by solid‐state NMR. The domain size of the dispersed phase assures a homogeneous distribution of POSS into the polymer, thus, a continuous phase corresponding to the organic matrix incorporates these nanometer‐sized POSS crosslinkers at a molecular level, in agreement with the transparency of the samples. The silicon–oxygen core framework has to be covalently bonded into the polymer backbone instead of being a simple additive and both the silica content and crosslinked degree exhibit a critical influence on the laser action.     

Secondary bioreceptivity of granite: effect of salt weathering on subaerial biofilm growth

Salt crystallisation is a very common and powerful weathering agent that can modify the petrophysical properties of building stone such as granite. In addition, the weathering can affect the susceptibility of the stone to biological colonisation. The aims of the present study were to examine the properties of a granite weathered by sodium chloride crystallisation and to evaluate the effects of the weathering on the secondary bioreceptivity of the stone to subaerial phototrophic biofilms. For this purpose, granite samples were subjected to a laboratory-based accelerated salt weathering test, and changes in weight, open porosity, bulk density, capillary water content, abrasion pH and surface roughness of the samples were determined. Samples of both weathered and non-weathered granite were then inoculated with a multi-species phototrophic culture derived from a natural subaerial biofilm and incubated under standardised laboratory conditions for 3 months. The weight loss produced by the weathering process was consistent with significant changes in abrasion pH and surface roughness. The bioreceptivity of the stone was also altered. According to the bioreceptivity index, the granite under study was characterised by ‘mild primary bioreceptivity’, but ‘high secondary bioreceptivity’ after the salt weathering process. Study of the secondary bioreceptivity of stone materials can provide very useful information about response to weathering effects, and the findings can be used to improve the selection of materials for building purposes.     

Co- and Ni-exchanged ferrierite: The contribution of synchrotron X-ray diffraction data to siting of TMIs

High-silica zeolites exchanged with transition metal ions (TMIs) are the subject of great interest for their unusual catalytic activity and selectivity. Structural information like coordination and accessibility of TMIs in zeolites are important factors for understanding their catalytic activity. Siting of TMIs in zeolites is typically obtained by spectroscopic (EXAFS, EPR, UV–vis and IR) and computational methods, as in the case of Co-ferrierite. However, some controversy exists in the literature concerning the model for incorporation of bare Co ions in ferrierite. We show here that the results of our synchrotron X-ray powder diffraction studies on Co- and Ni-exchanged ferrierite (Si/Al = 8.5) are in a good agreement with the model of Co siting based on an indirect spectroscopic approach and help to validate this model. By direct structural evidences, a possible explanation for the larger catalytic activity of Co sites in the main channels of ferrierite can be inferred. A combination of data from in situ XRD continuous monitoring of the Co ion migration during calcination and crystal-chemical considerations allows to device a strategy for the design of optimised co-cations containing Co-ferrierite catalysts.     

Designing and Rightsizing the Information System Architecture

Information system design and sizing constitute a complex, top-down process that tailors the technology architecture to application requirements. Practitioners usually tackle this top-down process by focusing on individual design aspects, such as data or specific applications, and by relying on their previous experiences to compare alternative architectural solutions. Acquisition costs are usually accounted for, but related operating and maintenance costs are often neglected or underestimated. The complexity of optimizing individual design problems leads researchers to avoid a global optimization perspective and, thus, the IS architecture is usually a result of the juxtaposition of multiple local optima.This paper takes an overall perspective on the cost minimization problem of information system design to achieve a better trade-off between cost and performance over the whole expected life of the technology architecture. A comprehensive design methodology is discussed as an integrating framework that accounts for all categories of costs, including design, implementation, maintenance, and operation, to achieve a globally cost-minimizing solution.     

PCBs and selected organochlorine compounds in Italian mountain air: the influence of altitude and forest ecosystem type

Passive air samplers (polyurethane foam disks) were deployed on an altitudinal transect in the rural Italian Alps to investigate the potential influence of forest cover on air concentrations. Samplers were exposed overtwo periods, each of several weeks, either in clearings or in forests. In the first period, there was high leaf coverage (high leaf area index, LAI); in the second, the LAI was low after the autumnal leaf fall. PCBs sequestered in the PUF generally declined with altitude, for example, in the clearings PCBs-28, 52, 90/101, 118, and 138, all showed statistically significant declines (p < 0.05). The mass of HCB sequestered increased with altitude, evidence of cold condensation. Ratios of the forest:clearing concentrations were calculated; this ratio expresses the filtering ability of forests to deplete air concentrations compared to the adjacent clearings. During the high LAI sampling period, these depletion factors ranged between 0.93 and 0.54 and were inversely correlated with temperature-corrected log K0A. This relationship was notobserved during the low LAI sampling period. The depletion factors were normalized using the LAI to give a density independent depletion factor (DIDF). The slopes of the correlations with K0A were comparable for broadleaf or coniferous forests at different altitudes, suggesting that leaf surfaces determine the exchanges with air. Broadleaf forests at 1000 and 1400 m showed similar behavior, while a conifer forest at 1800 m gave depletion factors which were higher by about a factor of 2. It is suggested that DIDF can be used in regional environmental fate models to estimate the contribution of forests to contaminant fate.     

Film Blowing of Biodegradable Polymer Nanocomposites for Agricultural Applications

Films for agricultural applications, such as greenhouses films or mulching films are generally made of polyolefins such as linear low-density polyethylene (LLDPE) or low-density polyethylene. However, the use of biodegradable and/or compostable polymers is increasing, which enjoy the additional advantage that they can be left on the site since a fine life would be gradually assimilated to the underlying soil. Nevertheless, biodegradable polymeric films often do not have suitable mechanical performances. In this work, biodegradable polymer-based nanocomposite films are prepared by film blowing and compared with traditional LLDPE based nanocomposites. In particular, a biodegradable polymer blend and two different inorganic nanofillers (an organo-modified clay and a calcium carbonate with a hydrophobic coating) are used for the preparation of the nanocomposites. A detailed investigation of obtained materials is performed through rheological, mechanical, and optical characterizations. Adding nanofillers led to an increase of rigidity and tear strength of blown films without negatively affecting their ductility.     

Easy Preparation of Liposome@PDA Microspheres for Fast and Highly Efficient Removal of Methylene Blue from Water

Mussel-inspired chemistry was usefully exploited here with the aim of developing a high-efficiency, environmentally friendly material for water remediation. A micro-structured material based on polydopamine (PDA) was obtained by using liposomes as templating agents and was used for the first time as an adsorbent material for the removal of methylene blue (MB) dye from aqueous solutions. Phospholipid liposomes were made by extrusion and coated with PDA by self-polymerization of dopamine under simple and mild conditions. The obtained Liposome@PDA microspheres were characterized by DLS and Zeta potential analysis, TEM microscopy, and FTIR spectroscopy. The effects of pH, temperature, MB concentration, amount of Liposome@PDA, and contact time on the adsorption process were investigated. Results showed that the highest adsorption capacity was obtained in weakly alkaline conditions (pH = 8.0) and that it could reach up to 395.4 mg g⁻¹ at 298 K. In addition, adsorption kinetics showed that the adsorption behavior fits a pseudo-second-order kinetic model well. The equilibrium adsorption data, instead, were well described by Langmuir isotherm. Thermodynamic analysis demonstrated that the adsorption process was endothermic and spontaneous (ΔG⁰ = −12.55 kJ mol⁻¹, ΔH⁰ = 13.37 kJ mol⁻¹) in the investigated experimental conditions. Finally, the applicability of Liposome@PDA microspheres to model wastewater and the excellent reusability after regeneration by removing MB were demonstrated.     

Multidrug Idebenone/Naproxen Co-loaded Aspasomes for Significant in vivo Anti-inflammatory Activity

The use of proper nanocarriers for dermal and transdermal delivery of anti-inflammatory drugs recently gained several attentions in the scientific community because they pass intact and accumulate payloads in the deepest layers of skin tissue. Ascorbyl palmitate-based vesicles (aspasomes) can be considered a promising nanocarrier for dermal and transdermal delivery due to their skin whitening properties and suitable delivery of payloads through the skin. The aim of this study was the synthesis of multidrug Idebenone/naproxen co-loaded aspasomes for the development of an effective anti-inflammatory nanomedicine. Aspasomes had suitable physicochemical properties and were safe in vivo if topically applied on human healthy volunteers. Idebenone/naproxen co-loaded aspasomes demonstrated an increased therapeutic efficacy of payloads compared to the commercially available Naprosyn® gel, with a rapid decrease of chemical-induced erythema on human volunteers. These promising results strongly suggested a potential application of Idebenone/naproxen multidrug aspasomes for the development of an effective skin anti-inflammatory therapy.