MgO Nanoparticles Obtained from an Innovative and Sustainable Route and Their Applications in Cancer Therapy.

This paper aimed to evaluate the biological damages towards diseased cells caused by the use of MgO nanoparticles (NPs). The NPs are produced by a calcination process of a precursor, which is an aqueous suspension of nanostructured Mg(OH)2, in turn synthesized following our original, time-energy saving and scalable method able to guarantee short times, high yield of production (up to almost 10 kg/week of NPs), low environmental impact and low energy demand. The MgO NPs, in the form of dry powders, are organized as a network of intercrystallite channels, in turn constituted by monodispersed and roughly spherical NPs < 10 nm, preserving the original pseudo hexagonal-platelet morphology of the precursor. The produced MgO powders are diluted in a PBS solution to obtain different MgO suspension concentrations that are subsequently put in contact, for 3 days, with melanoma and healthy cells. The viable count, made at 24, 48 and 72 h from the beginning of the test, reveals a good cytotoxic activity of the NPs, already at low MgO concentrations. This is particularly marked after 72 h, showing a clear reduction in cellular proliferation in a MgO-concentration-dependent manner. Finally, the results obtained on human skin fibroblasts revealed that the use MgO NPs did not alter at all both the vitality and proliferation of healthy cells.

New Eco-Friendly and Low-Energy Synthesis to Produce ZnO Nanoparticles for Real-World Scale Applications.

This paper presents an original and sustainable method for producing ZnO nanoparticles (NPs) in response to global challenges (low energy requirements, low environmental impact, short production times, and high production yield). The method is based on an ion exchange process between an anionic resin and an aqueous ZnCl2 solution; it operates in one step at room temperature/ambient pressure without the need for complex apparatus or purification steps. From the kinetics, we observed the formation of pure simonkolleite, a zinc-layered hydroxide salt (Zn5(OH)8Cl2·H2O), after only 5 min of reaction. This compound, used elsewhere as a ZnO precursor after calcination at high temperatures, here decomposes at room temperature into ZnO, allowing extraordinary savings of time and energy. Finally, in only 90 min, pure and crystalline ZnO NPs are obtained, with a production yield > 99%. Several types of aggregates resulting from the self-assembly of small hexagonal platelets (solid or hollow in shape) were observed. Using our revolutionary method, we produced almost 10 kg of ZnO NPs per week without any toxic waste, significantly reducing energy consumption; this method allows transferring the use of these unique NPs from the laboratory environment to the real world.

New Materials and Technologies for Durability and Conservation of Building Heritage.

The increase in concrete structures' durability is a milestone to improve the sustainability of buildings and infrastructures. In order to ensure a prolonged service life, it is necessary to detect the deterioration of materials by means of monitoring systems aimed at evaluating not only the penetration of aggressive substances into concrete but also the corrosion of carbon-steel reinforcement. Therefore, proper data collection makes it possible to plan suitable restoration works which can be carried out with traditional or innovative techniques and materials. This work focuses on building heritage and it highlights the most recent findings for the conservation and restoration of reinforced concrete structures and masonry buildings.

New Perspectives for the Consolidation of Mural Paintings in Hypogea with an Innovative Aqueous Nanolime Dispersion, Characterized by Compatible, Sustainable, and Eco-Friendly Features.

Consolidation of mural paintings in hypogea is challenging because of their severe microclimatic conditions, characterized by high humidity levels, low air circulation, the presence of salts efflorescence, and the detrimental growth of biodeteriogen agents. Traditional consolidant products show significant drawbacks when used in hypogeum. Organic compounds, such as acrylic emulsions, are bio-receptive and some inorganic consolidants, such as silica-based products, show a lack of compatibility with the original substrate, which could lead to a reduction in permeability and an increase in the mechanical resistance of the external layer. The presence of solvents in their formulations, particularly short-chain alcohols that can activate germination of fungal spores, leads to the release of great amounts of volatile organic compounds, which are particularly harmful in the hypogeic environment. To solve these problems, restorers of the Istituto Centrale per il Restauro (ICR) decided to use a new aqueous nanolime dispersion, NANOLAQ, consisting of pure and crystalline Ca(OH)2 nanoparticles dispersed in water, produced by an innovative and sustainable patented procedure. After laboratory testing, the product has been applied on site, on a medieval mural painting in the Ss. Peter and Paul hypogeum in the UNESCO site of Matera (Italy), monitoring the performance in terms of cohesion of the paint layer and preservation of aesthetic features.

New Sustainable, Scalable and One-Step Synthesis of Iron Oxide Nanoparticles by Ion Exchange Process.

This work introduces an innovative, sustainable, and scalable synthesis of iron oxides nanoparticles (NPs) in aqueous suspension. The method, based on ion exchange process, consists of a one-step procedure, time and energy saving, operating in water and at room temperature, by cheap and renewable reagents. The influence of both oxidation state of the initial reagent and reaction atmosphere is considered. Three kinds of iron nanostructured compounds are obtained (2-lines ferrihydrite; layered-structure iron oxyhydroxide δ-FeOOH; and cubic magnetite), in turn used as precursors to obtain hematite and maghemite NPs. All the produced NPs are characterized by a high purity, small particles dimensions (from 2 to 50 nm), and high specific surface area values up to 420 m2/g, with yields of production >90%. In particular, among the most common iron oxide NPs, we obtained cubic magnetite NPs at room temperature, characterized by particle dimensions of about 6 nm and a surface area of 170 m2/g. We also obtained hematite NPs at very low temperature conditions (that is 2 h at 200 °C), characterized by particles dimensions of about 5 nm with a surface area value of 200 m2/g. The obtained results underline the strength of the synthetic method to provide a new, sustainable, tunable, and scalable high-quality production.

Color Stability, Chemico-Physical and Optical Features of the Most Common PETG and PU Based Orthodontic Aligners for Clear Aligner Therapy.

It is difficult to find research papers collecting comparative results about characterization studies of clear aligners. Therefore, the aim of this paper is to provide the first comparative analysis of most commercial clear aligners, in terms of their stability towards intra-oral staining agents, their physicochemical and optical properties, as well as their water absorption behavior. Five types of aligners, characterized by different techniques, are considered: Erkodur, Essix Plastic, Ghost Aligner, Zendura, and Invisalign. The obtained results show that clear aligners are made up of PETG, semi rigid PU, and a mixture of PU and PETG, with different degrees of crystallinity which affect the transparency of each aligner. In particular, the PETG-based materials reveal the highest value of short-range order and the highest properties in terms of transparency in the visible range. After 14 days of immersion into red wine and coffee, PETG and PU-based aligners reveal a perceivable change in color (NBS values from 1.5 to 3), corresponding to a loss of transparency due to the deposition of impurities on the surface. These results are particularly marked for Invisalign, showing changes towards other colors (NBS up to 35), probably due to the thermoforming process which led to the formation of a wrinkled surface entrapping the impurities.

Sustainable Nanotechnologies for Curative and Preventive Wood Deacidification Treatments: An Eco-Friendly and Innovative Approach.

Waterlogged wooden artifacts represent an important historical legacy of our past. They are very fragile, especially due to the severe phenomenon of acidification that may occur in the presence of acid precursors. To date, a satisfactory solution for the deacidification of ancient wood on a large scale has still not been found. In this paper, we propose, for the first time, eco-friendly curative and preventive treatments using nanoparticles (NPs) of earth alkaline hydroxides dispersed in water and produced on a large scale. We present the characterization of the NPs (by X-ray diffraction, atomic-force and electron microscopy, and small-angle neutron scattering), together with the study of the deacidification efficiency of our treatments. We demonstrate that all our treatments are very effective for both curative and preventive aims, able to assure an almost neutral or slightly alkaline pH of the treated woods. Furthermore, the use of water as a solvent paves the way for large-scale and eco-friendly applications which avoid substances that are harmful for the environment and for human health.

Thermoplastic Disks Used for Commercial Orthodontic Aligners: Complete Physicochemical and Mechanical Characterization.

Invisible orthodontic aligners (IOAs) have been introduced in the orthodontic field as an innovative alternative for fixed brackets, in relation to their ability to be easily inserted/removed from the oral cavity without affecting the chewing ability and the aesthetic of the patients. The paper provides a complete physicochemical and mechanical characterization of thermoplastic materials in the form of disks used for commercial IOAs. A wide palette of specific techniques is considered, from tensile tests and dynamic-mechanical analysis, to X-Ray diffraction (XRD), differential scanning calorimetry (DSC), Fourier transformation infrared spectroscopy (FTIR-ATR) analyses and water absorption tests. The disks are investigated before and after immersion into staining beverages (red wine, coffee, nicotine and artificial saliva), in terms of colour variations, transparency, and microscopic surface modifications by means of colorimetry, UV-VIS absorbance and scanning electron microscopy (SEM). Among all the samples, polyurethane (PU) exhibited the highest crystallinity and the highest values of mechanical and thermal resistance, while the poly(ethylene terephthalate)-glycol (PETG) samples presented better transparency and less ability to absorb water. Moreover, red wine and coffee give noticeable colour variations after 14 days of immersion, together with a slight reduction of transparency.

Nano-Sized Fe(III) Oxide Particles Starting from an Innovative and Eco-Friendly Synthesis Method.

This paper introduces an original, eco-friendly and scalable method to synthesize ferrihydrite nanoparticles in aqueous suspensions, which can also be used as a precursor to produce α-hematite nanoparticles. The method, never used before to synthesize iron oxides, is based on an ion exchange process allowing to operate in one-step, with reduced times, at room temperature and ambient pressure, and using cheap or renewable reagents. The influence of reagent concentrations and time of the process on the ferrihydrite features is considered. The transformation to hematite is then analyzed and discussed in relation to different procedures: (1) A natural aging in the water at room temperature; and (2) heat treatments at different temperatures and times. Structural and morphological features of the obtained nanoparticles are investigated by means of several techniques, such as X-ray diffraction, X-ray photoelectron spectroscopy, attenuated total reflectance Fourier transform infrared spectroscopy, transmission and scanning electron microscopy, thermal analysis, nitrogen adsorption and magnetic measurements. Ferrihydrite shows the typical spherical morphology and a very high specific surface area of 420 m2/g. Rhombohedral or plate-like hexagonal hematite nanoparticles are obtained by the two procedures, characterized by dimensions of 50 nm and 30 nm, respectively, and a specific surface area up to 57 m2/g, which is among the highest values reported in the literature for hematite NPs.

Binders alternative to Portland cement and waste management for sustainable construction-part 1.

This review presents "a state of the art" report on sustainability in construction materials. The authors propose different solutions to make the concrete industry more environmentally friendly in order to reduce greenhouse gases emissions and consumption of non-renewable resources. Part 1-the present paper-focuses on the use of binders alternative to Portland cement, including sulfoaluminate cements, alkali-activated materials, and geopolymers. Part 2 will be dedicated to traditional Portland-free binders and waste management and recycling in mortar and concrete production.

Binders alternative to Portland cement and waste management for sustainable construction - Part 2.

The paper represents the "state of the art" on sustainability in construction materials. In Part 1 of the paper, issues related to production, microstructures, chemical nature, engineering properties, and durability of mixtures based on binders alternative to Portland cement were presented. This second part of the paper concerns the use of traditional and innovative Portland-free lime-based mortars in the conservation of cultural heritage, and the recycling and management of wastes to reduce consumption of natural resources in the production of construction materials. The latter is one of the main concerns in terms of sustainability since nowadays more than 75% of wastes are disposed of in landfills.

Assessing the transport rate of hyperpolarized pyruvate and lactate from the intra- to the extracellular space.

The use of [1-(13) C]pyruvate hyperpolarized by means of dynamic nuclear polarization provides a direct way to track the metabolic transformations of this metabolite in vivo and in cell cultures. The identification of the intra- and extracellular contributions to the (13) C NMR resonances is not straightforward. In order to obtain information about the rate of pyruvate and lactate transport through the cellular membrane, we set up a method that relies on the sudden 'quenching' of the extracellular metabolites' signal. The paramagnetic Gd-tetraazacyclododecane triacetic acid (Gd-DO3A) complex was used to dramatically decrease the longitudinal relaxation time constants of the (13) C-carboxylate resonances of both pyruvate and lactate. When Gd-DO3A was added to an MCF-7 cellular culture, which had previously received a dose of hyperpolarized [1-(13) C]pyruvate, the contributions of the extracellular pyruvate and lactate signals were deleted. From the analysis of the decay curves of the (13) C-carboxylate resonances of pyruvate and lactate it was possible to extract information about the exchange rate of the two metabolites across the cellular membrane. In particular, it was found that, in the reported experimental conditions, the lactate transport from the intra- to the extracellular space is not much lower than the rate of lactate formation. The method reported herein is non-destructive and it could be translated to in vivo studies. It opens a route for the use of hyperpolarized pyruvate to assess altered activity of carboxylate transporter proteins that may occur in pathological conditions. Copyright © 2016 John Wiley & Sons, Ltd.

Probing lactate secretion in tumours with hyperpolarised NMR.

Most tumours exhibit a high rate of glycolysis and predominantly produce energy by lactic acid fermentation. To maintain energy production and prevent toxicity, the lactate generated needs to be rapidly transported out of the cell. This is achieved by monocarboxylate transporters (MCTs), which therefore play an essential role in cancer metabolism and development. In vivo experiments were performed on eight male Fisher F344 rats bearing a subcutaneous mammary carcinoma after injection of hyperpolarised [1-(13) C]pyruvate. A Gd(III)DO3A complex that binds to pyruvate and its metabolites was used to efficiently destroy the extracellular magnetisation after hyperpolarised lactate had been formed. Moreover, a pulse sequence including a frequency-selective saturation pulse was designed so that the pyruvate magnetisation could be destroyed to exclude effects arising from further conversion. Given this preparation, metabolite transport out of the cell manifested as additional decay and apparent cell membrane transporter rates could thus be obtained using a reference measurement without a relaxation agent. In addition to slice-selective spectra, spatially resolved maps of apparent membrane transporter activity were acquired using a single-shot spiral gradient readout. A considerable increase in decay rate was detected for lactate, indicating rapid transport out of the cell. The alanine signal was unaltered, which corresponds to a slower efflux rate. This technique could allow for better understanding of tumour metabolism and progression, and enable treatment response measurements for MCT-targeted cancer therapies. Moreover, it provides vital insights into the signal kinetics of hyperpolarised [1-(13) C]pyruvate examinations. Copyright © 2016 John Wiley & Sons, Ltd.

Single-Scan Multidimensional NMR Analysis of Mixtures at Sub-Millimolar Concentrations by using SABRE Hyperpolarization.

Signal amplification by reversible exchange (SABRE) is a promising method to increase the sensitivity of nuclear magnetic resonance (NMR) experiments. However, SABRE-enhanced (1)H NMR signals are short lived, and SABRE is often used to record 1D NMR spectra only. When the sample of interest is a complex mixture, this results in severe overlaps for (1)H spectra. In addition, the use of a co-substrate, whose signals may obscure the (1) H spectra, is currently the most efficient way to lower the detection limit of SABRE experiments. Here, we describe an approach to obtain clean, SABRE-hyperpolarized 2D (1)H NMR spectra of mixtures of small molecules at sub-millimolar concentrations in a single scan. The method relies on the use of para-hydrogen together with a deuterated co-substrate for hyperpolarization and ultrafast 2D NMR for acquisition. It is applicable to all substrates that can be polarized with SABRE.