Geopolymer-Based Materials for the Removal of Ibuprofen: A Preliminary Study.

Every year, new compounds contained in consumer products, such as detergents, paints, products for personal hygiene, and drugs for human and veterinary use, are identified in wastewater and are added to the list of molecules that need monitoring. These compounds are indicated with the term emerging contaminants (or Contaminants of Emerging Concern, CECs) since they are potentially dangerous for the environment and human health. To date, among the most widely used methodologies for the removal of CECs from the aquatic environment, adsorption processes play a role of primary importance, as they have proven to be characterized by high removal efficiency, low operating and management costs, and an absence of undesirable by-products. In this paper, the adsorption of ibuprofen (IBU), a nonsteroidal anti-inflammatory drug widely used for treating inflammation or pain, was performed for the first time using two different types of geopolymer-based materials, i.e., a metakaolin-based (GMK) and an organic-inorganic hybrid (GMK-S) geopolymer. The proposed adsorbing matrices are characterized by a low environmental footprint and have been easily obtained as powders or as highly porous filters by direct foaming operated directly into the adsorption column. Preliminary results demonstrated that these materials can be effectively used for the removal of ibuprofen from contaminated water (showing a concentration decrease of IBU up to about 29% in batch, while an IBU removal percentage of about 90% has been reached in continuous), thus suggesting their potential practical application.

Measurement of gravitational and thermal effects in a liquid-actuated torsion pendulum.

We describe a proof-of-principle experiment aiming to investigate the inverse-square law of gravitation at the centimeter scale. The sensor is a two-stage torsion pendulum, while actuation is accomplished by a variable liquid mass. The time-varying gravitational force is related to the level of the circulating fluid in one or two containers at a short distance from the test mass, with all moving mechanical parts positioned at a large distance. We provide a description of the apparatus and present the first results. We identified a systematic effect of thermal origin, producing offsets of few fNm in torque and of about 10 pN in force. When this effect is neutralized, the measurements agree well with the predictions of simulations. We also discuss the upcoming instrument upgradations and the expected sensitivity improvement that will allow us to perform measurements with adequate accuracy to investigate the unexplored regions of the α-λ parameter space of a Yukawa-like deviation from the Newtonian potential.

Evidence of Small Fungal Cysteine-Rich Proteins Acting as Biosurfactants and Self-Assembling into Large Fibers.

Fungi produce surface-active proteins, among which hydrophobins are the most characterized and attractive also for their ability to form functional amyloids. Our most recent findings show that these abilities are shared with other classes of fungal proteins. Indeed, in this paper, we compared the characteristics of a class I hydrophobin (Vmh2 from Pleurotus ostreatus) and an unknown protein (named PAC3), extracted from the marine fungal strain Acremonium sclerotigenum, which does not belong to the same protein family based on its sequence features. They both proved to be good biosurfactants, stabilizing emulsions in several conditions (concentration, pH, and salinity) and decreasing surface tension to a comparable value to that of some synthetic surfactants. After that, we observed for both Vmh2 and PAC3 the formation of giant fibers without the need for harsh conditions or long incubation time, a remarkable ability herein reported for the first time.

Development of Geopolymer-Based Materials with Ceramic Waste for Artistic and Restoration Applications.

This contribution presents the preparation and characterization of new geopolymer-based mortars obtained from recycling waste deriving from the production process and the "end-of-life" of porcelain stoneware products. Structural, morphological, and mechanical studies carried out on different kinds of mortars prepared by using several types of by-products (i.e., pressed burnt and extruded ceramic waste, raw pressed and gypsum resulting from exhausted moulds) point out that these systems can be easily cast, also in complex shapes, and show a more consistent microstructure with respect to the geopolymer paste, with a reduced amount of microcracks. Moreover, the excellent adhesion of these materials to common substrates such as pottery and earthenware, even for an elevated concentration of filler, suggests their use in the field of technical-artistic value-added applications, such as restoration, conservation, and/or rehabilitation of historic monuments, or simply as materials for building revetments. For all these reasons, the proposed materials could represent valuable candidates to try to overcome some problems experienced in the cultural heritage sector concerning the selection of environmentally friendly materials that simultaneously meet art and design technical requirements.

Sustainable Materials Based on Geopolymer-Polyvinyl Acetate Composites for Art and Design Applications.

The recent introduction of the Next Generation EU packages on the circular economy and the Italian Ecological Transition Plan has further boosted the research of effective routes to design materials with low energy and low environmental impact, in all areas of research, including art and design and cultural heritage. In this work, we describe for the first time the preparation and characterization of a new sustainable adhesive material to be used in the art and design sector, consisting of a geopolymer-based composite with polyvinyl acetate (PVAc), both considered more environmentally acceptable than the analogous inorganic or polymeric materials currently used in this sector. The key idea has been the development of organic-inorganic composites by reacting low molecular weight polymers with the geopolymer precursor to obtain a material with reduced brittleness and enhanced adhesion with common substrates. Structural, morphological, and mechanical studies pointed out the consistent microstructure of the composite materials if compared to the neat geopolymer, showing lower density (up to 15%), improved flexural strength (up to 30%), similar water absorption and a relevant toughening effect (up to 40%). Moreover, the easy pourability in complex shapes and the excellent adhesion of these materials to common substrates suggest their use as materials for restoration, rehabilitation of monuments, and decorative and architectural intervention. The organic-inorganic nature of these new materials also makes them easily recognizable from the support on which they are used, favoring, in line with the dictates of good restoration practices, their possible complete removal. For all these reasons, these new materials could represent promising candidates to overcome the limits related to the creative industry for what concerns the selection of environmentally friendly materials to meet design requirements with low environmental impacts.

Homogeneous Catalysis and Heterogeneous Recycling: A Simple Zn(II) Catalyst for Green Fatty Acid Esterification.

This work describes the use of simple zinc(II) salts (ZnCl2, ZnCO3, Zn(OAc)2, ZnO, Zn(ClO4)2, Zn(TfO)2, and Zn(BF4)2) as effective catalysts for the esterification of fatty acids with long-chain alcohols and simple polyols through a homogeneous system that allows the gradual and selective removal of water. The results show that the catalytic activity depends on the nature of the counterion: the most effective are the salts with poorly coordinating anions (perchlorate and triflate) or containing basic Brønsted anions (oxide, acetate, and carbonate). However, only with the latter is it possible to fully recover the catalyst at the end of each run, which is easily filtered in the form of zinc carboxylate, given its insolubility in the ester produced. In this way, it is possible to recycle the catalyst numerous times, without any loss of activity. This beneficial prerogative couples the efficiency of the homogeneous catalysis with the advantage of the heterogeneous catalysis. The process is, therefore, truly sustainable, given its high efficiency, low energy consumption, ease of purification, and the absence of auxiliary substances and byproducts.

Towards the Development of Antioxidant Cerium Oxide Nanoparticles for Biomedical Applications: Controlling the Properties by Tuning Synthesis Conditions.

In this work CeO2 nanoparticles (CeO2-NPs) were synthesized through the thermal decomposition of Ce(NO3)3·6H2O, using as capping agents either octylamine or oleylamine, to evaluate the effect of alkyl chain length, an issue at 150 °C, in the case of octylamine and at 150 and 250 °C, in the case of oleylamine, to evaluate the effect of the temperature on NPs properties. All the nanoparticles were extensively characterized by a multidisciplinary approach, such as wide-angle X-ray diffraction, transmission electron microscopy, dynamic light scattering, UV-Vis, fluorescence, Raman and FTIR spectroscopies. The analysis of the experimental data shows that the capping agent nature and the synthesis temperature affect nanoparticle properties including size, morphology, aggregation and Ce3+/Ce4+ ratio. Such issues have not been discussed yet, at the best of our knowledge, in the literature. Notably, CeO2-NPs synthesized in the presence of oleylamine at 250 °C showed no tendency to aggregation and we made them water-soluble through a further coating with sodium oleate. The obtained nanoparticles show a less tendency to clustering forming stable aggregates (ranging between 14 and 22 nm) of few NPs. These were tested for biocompatibility and ROS inhibiting activity, demonstrating a remarkable antioxidant activity, against oxidative stress.

Coral-like plasmonic probes for tip-enhanced Raman spectroscopy.

Tip-enhanced Raman spectroscopy is a powerful tool for the analysis of system interfaces, enabling access to chemical information with nanometric spatial resolution and sensitivity up to the single molecule level. Such features are due to the presence of proper metallic nanostructures at the TERS probe apex, which, via the excitation of a plasmonic field, confine light to a nanometric region. The nano-sized characteristic of such metallic structures intrinsically renders the fabrication of high performing and reproducible TERS probes still a challenge. In this paper, we present a facile, rapid and effective approach to prepare Ag-based TERS probes. The fabrication process proposed herein is based on spinodal dewetting of Ag-coated AFM-probes through a RF plasma treatment. The obtained probes appear covered with a coral-like silver nanotexture, endowed with an excellent plasmonic activity. Intriguingly, such a texture can be easily tuned by changing some process parameters, such as Ag film thickness and exposure time to the plasma. The as-prepared TERS probes show a high TERS enhancement, reaching 107, and allow a good spatial resolution, down to 10 nm. Finally, we suggest an easy and effective procedure to restore oxidized TERS tips following exposure to ambient air, which can be applied to all types of Ag-based TERS tips.

Nanocomposites of Au/Disentangled UHMWPE: A Combined Optical and Structural Study.

The term disentangled refers to polymers with fewer entanglements in the amorphous regions, a metastable condition that can significantly affect the material's properties and processing behavior. The lower entanglement density in ultra-high molecular weight polyethylene (dis-UHMWPE) facilitates the solid-state processability into uniaxially-oriented specimens reaching very high draw ratios and crystallinities. In this study, Au/dis-UHMWPE nanocomposites were formulated and processed at variable draw ratios. Polarized light microscopy suggests gold nanoparticles are oriented in arrays following the drawing of polymer chains. The structural features, upon orientation, are studied by means of Raman spectroscopy, wide- and small-angle X-ray scattering, and near-infrared spectrophotometry. Crystallinity is found to increase by 15%, as calculated by wide-angle X-ray scattering. The change in optical absorbance in the visible spectrum indicates that, with orientation, the average size of gold aggregates increases, supported quantitatively by small-angle X-ray scattering. Since the gold nanoparticles are expected to be found within amorphous chain segments, the aforementioned findings are attributed to the increase of crystallinity and thus the decrease of available (amorphous) space.

Hybrid Fly Ash-Based Geopolymeric Foams: Microstructural, Thermal and Mechanical Properties.

This research investigates the preparation and characterization of new organic-inorganic geopolymeric foams obtained by simultaneously reacting coal fly ash and an alkali silicate solution with polysiloxane oligomers. Foaming was realized in situ using Si0 as a blowing agent. Samples with density ranging from 0.3 to 0.7 g/cm3 that show good mechanical properties (with compressive strength up to ≈5 MPa for a density of 0.7 g/cm3) along with thermal performances (λ = 0.145 ± 0.001 W/m·K for the foamed sample with density 0.330 g/cm3) comparable to commercial lightweight materials used in the field of thermal insulation were prepared. Since these foams were obtained by valorizing waste byproducts, they could be considered as low environmental impact materials and, hence, with promising perspectives towards the circular economy.

Hybrid Geopolymeric Foams for the Removal of Metallic Ions from Aqueous Waste Solutions.

For the first time, hybrid organic-inorganic geopolymeric foams were successfully used as monolithic adsorbents for the removal of metallic ions pollutants from wastewaters. The foams were realized by the in situ foaming of a hybrid geopolymer obtained by a reaction of metakaolin and polysiloxane oligomers under strong alkaline conditions and then cured at room temperature. In this way, porous materials with densities ranging from 0.4 to 0.7 g/cm3 and showing good mechanical properties were produced. With the aim of producing self-standing monolithic adsorbents for the removal of metallic ions pollutants from wastewaters, these porous hybrid geopolymers were subjected to a washing pretreatment with ultrapure water, dried, and then used for absorption tests by dipping them into an aqueous solution with an initial concentration of 20 ppm of Pb2+, Cd2+, Cu2+, and Zn2+ ions. Preliminary results indicated that all the tested materials are effective in the adsorption of the tested metal ions and do not release the removed metal ions upon sinking in ultrapure water, even for a very long time. Interestingly, compressive strength tests performed before and after the washing treatments show that the foamed samples remain intact and maintain their physical-mechanical characteristics, suggesting that these kinds of materials are promising candidates for the production of self-standing, monolithic adsorbent substrates that can be easily collected when exhausted, which is a major advantage in comparison with the use of powdered adsorbents. Moreover, since these materials can be obtained by a simple and versatile experimental procedure, they could be easily shaped or directly foamed into precast molds to be used in packed beds as membranes.

Hybrid Geopolymers from Fly Ash and Polysiloxanes.

The preparation and characterization of innovative organic-inorganic hybrid geopolymers, obtained by valorizing coal fly ash generated from thermoelectric power plants, is reported for the first time. These hybrid materials are prepared by simultaneously reacting fly ash and dimethylsiloxane oligomers at 25 °C in a strongly alkaline environment. Despite their lower density, the obtained materials are characterized by highly improved mechanical properties when compared to the unmodified geopolymer obtained without the use of polysiloxanes, hence confirming the effectiveness of the applied synthetic strategy which specifically aims at obtaining hybrid materials with better mechanical properties in respect to conventional ones. This study is an example of the production of new materials by reusing and valorizing waste raw resources and by-products, thus representing a possible contribution towards the circular economy.

Encapsulation of inuloxin A, a plant germacrane sesquiterpene with potential herbicidal activity, in ß-cyclodextrins.

Inuloxin A is a promising plant phytotoxic sesquiterpene that deserves further studies to evaluate its potential as a bioherbicide. However, its low solubility in water and its bioavailability could hamper its practical applications. For this reason, inuloxin A was complexed with ß-cyclodextrins by using three different methods, i.e., kneading, co-precipitation and grinding. The resulted complexes were fully characterized by different techniques such as 1H NMR, UV-vis, XRD, DSC and SEM, and they were biologically assayed in comparison with the pure compound in several biological systems. The efficacy of the kneading and grinding complexes was similar to that of inuloxin A and these complexes almost completely inhibit Phelipanche ramosa seed germination. The complete solubility in water and the preservation of the biological properties of these two complexes could allow further studies to develop a novel natural herbicide for parasitic plant management based on these formulations.

Innovative Fly Ash Geopolymer-Epoxy Composites: Preparation, Microstructure and Mechanical Properties.

The preparation and characterization of composite materials based on geopolymers obtained from fly ash and epoxy resins are reported for the first time. These materials have been prepared through a synthetic method based on the concurrent reticulation of the organic and inorganic components that allows the formation of hydrogen bonding between the phases, ensuring a very high compatibility between them. These new composites show significantly improved mechanical properties if compared to neat geopolymers with the same composition and comparable performances in respect to analogous geopolymer-based composites obtained starting from more expensive raw material such as metakaolin. The positive combination of an easy synthetic approach with the use of industrial by-products has allowed producing novel low cost aluminosilicate binders that, thanks to their thixotropicity and good adhesion against materials commonly used in building constructions, could be used within the field of sustainable building.

Synthesis and characterizations of melamine-based epoxy resins.

A new, easy and cost-effective synthetic procedure for the preparation of thermosetting melamine-based epoxy resins is reported. By this innovative synthetic method, different kinds of resins can be obtained just by mixing the reagents in the presence of a catalyst without solvent and with mild curing conditions. Two types of resins were synthesized using melamine and a glycidyl derivative (resins I) or by adding a silane derivative (resin II). The resins were characterized by means of chemical-physical and thermal techniques. Experimental results show that all the prepared resins have a good thermal stability, but differ for their mechanical properties: resin I exhibits remarkable stiffness with a storage modulus value up to 830 MPa at room temperature, while lower storage moduli were found for resin II, indicating that the presence of silane groups could enhance the flexibility of these materials. The resins show a pot life higher than 30 min, which makes these resins good candidates for practical applications. The functionalization with silane terminations can be exploited in the formulation of hybrid organic-inorganic composite materials.

Synthesis and Characterization of Novel Epoxy Geopolymer Hybrid Composites.

The preparation and the characterization of novel geopolymer-based hybrid composites are reported. These materials have been prepared through an innovative synthetic approach, based on a co-reticulation in mild conditions of commercial epoxy based organic resins and a metakaolin-based geopolymer inorganic matrix. This synthetic strategy allows the obtainment of a homogeneous dispersion of the organic particles in the inorganic matrix, up to 25% in weight of the resin. The materials obtained present significantly enhanced compressive strengths and toughness with respect to the neat geopolymer, suggesting their wide utilization for structural applications. A preliminary characterization of the porous materials obtained by removing the organic phase from the hybrid composites by means of heat treatments is also reported. Possible applications of these materials in the field of water purification, filtration, or as lightweight insulating materials are envisaged.

Crystal structure of the trigonal form of isotactic polypropylene as an example of density-driven polymer structure.

Propene-hexene copolymers crystallize in a new polymorphic form of isotactic polypropylene when the concentration of hexene is higher than nearly 10-15 mol %. The hexene units are included in the crystals, inducing an increase of density that allows crystallization of 3-fold helical chains in a trigonal unit cell according to the space group R3c or Rc, where the helical symmetry of the chains is maintained in the crystal lattice. The structure of this new form is similar to those of isotactic polybutene and polystyrene and does not crystallize in polypropylene homopolymer because it would have too low density. The crystal structure of isotactic polypropylene is therefore no longer an exception to the principles of polymer crystallography, but the new structure represents the fulfillment of these principles and indicates that the packing of polymer molecules is mainly driven by density.