Ce-radical Scavenger-Based Perfluorosulfonic Acid Aquivion® Membrane for Pressurised PEM Electrolysers.

A Ce-radical scavenger-based perfluorosulfonic acid (PFSA) Aquivion® membrane (C98 05S-RSP) was developed and assessed for polymer electrolyte membrane (PEM) electrolyser applications. The membrane, produced by Solvay Specialty Polymers, had an equivalent weight (EW) of 980 g/eq and a thickness of 50 µm to reduce ohmic losses at a high current density. The electrochemical properties and gas crossover through the membrane were evaluated upon the formation of a membrane-electrode assembly (MEA) in a range of temperatures between 30 and 90 °C and at various differential pressures (ambient, 10 and 20 bars). Bare extruded (E98 05S) and reinforced (R98 05S) PFSA Aquivion® membranes with similar EWs and thicknesses were assessed for comparison in terms of their performance, stability and hydrogen crossover under the same operating conditions. The method used for the membrane manufacturing significantly influenced the interfacial properties, with the electrodes affecting the polarisation resistance and H2 permeation in the oxygen stream, as well as the degradation rate, as observed in the durability studies.

Geopolymers and Functionalization Strategies for the Development of Sustainable Materials in Construction Industry and Cultural Heritage Applications: A Review.

In the last decades, new synthetic hybrid materials, with an inorganic and organic nature, have been developed to promote their application as protective coatings and/or structural consolidants for several substrates in the construction industry and cultural heritage field. In this context, the scientific community paid attention to geopolymers and their new hybrid functional derivatives to design and develop innovative and sustainable composites with better chemical resistance, durability and mechanical characteristics. This review offers an overview of the latest progress in geopolymer-based hybrid nanofunctional materials and their use to treat and restore cultural heritage, as well as their employment in the building and architectural engineering field. In addition, it discusses the influence of some parameters, such as the chemical and physical characteristics of the substrates, the dosage of the alkaline activator, and the curing treatment, which affect their synthesis and performance.

Synthesis, Chemical-Physical Characterization, and Biomedical Applications of Functional Gold Nanoparticles: A Review.

Relevant properties of gold nanoparticles, such as stability and biocompatibility, together with their peculiar optical and electronic behavior, make them excellent candidates for medical and biological applications. This review describes the different approaches to the synthesis, surface modification, and characterization of gold nanoparticles (AuNPs) related to increasing their stability and available features useful for employment as drug delivery systems or in hyperthermia and photothermal therapy. The synthetic methods reported span from the well-known Turkevich synthesis, reduction with NaBH4 with or without citrate, seeding growth, ascorbic acid-based, green synthesis, and Brust-Schiffrin methods. Furthermore, the nanosized functionalization of the AuNP surface brought about the formation of self-assembled monolayers through the employment of polymer coatings as capping agents covalently bonded to the nanoparticles. The most common chemical-physical characterization techniques to determine the size, shape and surface coverage of AuNPs are described underlining the structure-activity correlation in the frame of their applications in the biomedical and biotechnology sectors.

Nanostructured Surface Finishing and Coatings: Functional Properties and Applications.

This review presents current literature on different nanocomposite coatings and surface finishing for textiles, and in particular this study has focused on smart materials, drug-delivery systems, industrial, antifouling and nano/ultrafiltration membrane coatings. Each of these nanostructured coatings shows interesting properties for different fields of application. In this review, particular attention is paid to the synthesis and the consequent physico-chemical characteristics of each coating and, therefore, to the different parameters that influence the substrate deposition process. Several techniques used in the characterization of these surface finishing coatings were also described. In this review the sol-gel method for preparing stimuli-responsive coatings as smart sensor materials is described; polymers and nanoparticles sensitive to pH, temperature, phase, light and biomolecules are also treated; nanomaterials based on phosphorus, borates, hydroxy carbonates and silicones are used and described as flame-retardant coatings; organic/inorganic hybrid sol-gel coatings for industrial applications are illustrated; carbon nanotubes, metallic oxides and polymers are employed for nano/ultrafiltration membranes and antifouling coatings. Research institutes and industries have collaborated in the advancement of nanotechnology by optimizing conversion processes of conventional materials into coatings with new functionalities for intelligent applications.

Development of Antibacterial and Antifouling Innovative and Eco-Sustainable Sol-Gel Based Materials: From Marine Areas Protection to Healthcare Applications.

Bacterial colonization of surfaces is the leading cause of deterioration and contaminations. Fouling and bacterial settlement led to damaged coatings, allowing microorganisms to fracture and reach the inner section. Therefore, effective treatment of surface damaged material is helpful to detach bio-settlement from the surface and prevent deterioration. Moreover, surface coatings can withdraw biofouling and bacterial colonization due to inherent biomaterial characteristics, such as superhydrophobicity, avoiding bacterial resistance. Fouling was a past problem, yet its untargeted toxicity led to critical environmental concerns, and its use became forbidden. As a response, research shifted focus approaching a biocompatible alternative such as exciting developments in antifouling and antibacterial solutions and assessing their antifouling and antibacterial performance and practical feasibility. This review introduces state-of-the-art antifouling and antibacterial materials and solutions for several applications. In particular, this paper focuses on antibacterial and antifouling agents for concrete and cultural heritage conservation, antifouling sol-gel-based coatings for filtration membrane technology, and marine protection and textile materials for biomedicine. In addition, this review discusses the innovative synthesis technologies of antibacterial and antifouling solutions and the consequent socio-economic implications. The synthesis and the related physico-chemical characteristics of each solution are discussed. In addition, several characterization techniques and different parameters that influence the surface finishing coatings deposition were also described.

Removal of As(III) from Biological Fluids: Mono- versus Dithiolic Ligands.

Arsenic is one of the inorganic pollutants typically found in natural waters, and its toxic effects on the human body are currently of great concern. For this reason, the search for detoxifying agents that can be used in a so-called "chelation therapy" is of primary importance. However, to the aim of finding the thermodynamic behavior of efficient chelating agents, extensive speciation studies, capable of reproducing physiological conditions in terms of pH, temperature, and ionic strength, are in order. Here, we report on the acid-base properties of meso-2,3-dimercaptosuccinic acid (DMSA) at different temperatures (i.e., T = 288.15, 298.15, 310.15, and 318.15 K). In particular, its capability to interact with As(III) has been investigated by experimentally evaluating some crucial thermodynamic parameters (ΔH and TΔS), stability constants, and its speciation model. Additionally, in order to gather information on the microscopic coordination modalities of As(III) with the functional groups of DMSA and, at the same time, to better interpret the experimental results, a series of state-of-the-art ab initio molecular dynamics simulations have been performed. For the sake of completeness, the sequestering capabilities of DMSA-a simple dithiol ligand-toward As(III) are directly compared with those recently emerged from similar analyses reported on monothiol ligands.

Interaction between As(III) and Simple Thioacids in Water: An Experimental and ab Initio Molecular Dynamics Investigation.

Albeit arsenic compounds are ubiquitous in aqueous solutions, the speciation of such a pollutant in natural water mainly depends on its binding capabilities with specific molecules. The features of most of the interactions of arsenic complexes can be established in solution, but the data related to the stability of the formed species, essentially depending on the concentration of the ligands, are elusive. For this reason, here, we report on a series of investigations where diverse approaches are combined together in order to characterize the behavior of As(III) species in aqueous solutions where simple chelating agents, such as thiolactic and thiomalic acids, are solvated. By synergistically exploiting potentiometric, calorimetric, and spectroscopic measurements along with ab initio molecular dynamics, the stability and the underlying formation mechanisms of specific species, along with the arsenic coordination modalities with the ligands, have macroscopically and microscopically been assessed. Furthermore, vibrational modes of the complexes formed by arsenic and simple thioacids have been assigned by means of Raman experiments.

Study of Al3+ interaction with AMP, ADP and ATP in aqueous solution.

The interaction of Al3+ and nucleotide ligands, namely adenosine-5'-monophosphate, (AMP), adenosine-5'-diphosphate, (ADP), adenosine-5'-triphosphate, (ATP), has been studied in aqueous solution at T = 298.15 K and I = 0.15 mol L-1 in NaCl (only for Al3+-ATP system at I = 0.1 mol L-1). Formation constants and speciation models for the species formed are discussed on the basis of potentiometric results. The speciation models found for the three systems include ML and ML2 species in all the cases, and for Al3+-ADP and ATP systems, MLH, MLOH and ML2OH species as well. The formation constant value for ML species shows the trend, AMP < ADP < ATP. 1H NMR spectroscopy was also employed for the study of Al3+-ATP system. The 1H NMR results are in agreement with the speciation model obtained from analysis of potentiometric titration data, confirming the stabilities of the main species. Enthalpy change values were obtained by titration calorimetry; for the main Al3+-ATP species (at T = 298.15 K and I = 0.1 mol L-1 in NaCl), they resulted always higher than zero, as typical for hard-hard interactions. The dependence of formation constants on ionic strength over the range I = 0.1 to 1 mol L-1 in NaCl is also reported for Al3+-ATP system. The sequestering ability of the nucleotides under study towards Al3+ was also evaluated by the empirical parameter pL0.5.

Sequestration of Aluminium(III) by different natural and synthetic organic and inorganic ligands in aqueous solution.

The speciation of Al3+ in aqueous solutions containing organic and inorganic ligands important from a biological (citrate (Cit3-), gluconate (Gluc-), lactate (Lac-), silicate (H2SiO42-), carbonate (CO32-), fluoride (F-)) and industrial (Gantrez®; polymethyl-vinyl-ether-co-maleic acids; GTZ S95 and GTZ AN169) point of view is reported. The stability constants of Al3+/Lz- complexes (Lz- = ligand with z- charge) were determined by potentiometry at T = 298.15 K and 0.10 ≤ I/M ≤ 1.00 in NaCl(aq) (in NaNO3(aq) only for Al3+/GTZ S95 and Al3+/Gluc- acid systems). For Al3+/Cit3-, Al3+/Lac- and Al3+/GTZ AN1694- systems, the investigations were also carried out at 283.15 ≤ T/K ≤ 318.15. The dependence of the thermodynamic parameters on ionic strength and temperature was modelled with a Debye-Hückel type equation. Different speciation schemes of Al3+/Lz- systems were obtained, including protonated, simple metal-ligand, polynuclear and hydrolytic mixed species. At I → 0 M and T = 298.15 K the stability trend for the AlL(3-z) species is: 14.28 ± 0.02, 13.99 ± 0.03, 10.16 ± 0.03, 3.16 ± 0.08, 2.84 ± 0.10 for GTZ S95, GTZ AN169, Cit3-, Gluc- and Lac-, respectively. From the investigations at different temperatures, it results that the entropic contribution is the driving force of the reactions. The sequestering ability of the ligands towards Al3+ was investigated determining the pL0.5 parameter at different experimental conditions, finding the following trend: Cit3- ¼ Gluc- > GTZ S954- > GTZ AN1694- > Lac- for the organic ligands, and pL0.5: F- ¼ CO32- > H2SiO42- for the inorganic ones.

Thermodynamic and spectroscopic study of Al3+ interaction with glycine, l-cysteine and tranexamic acid in aqueous solution.

In this paper a thermodynamic and spectroscopic study on the interaction between Al3+ and glycine (Gly), l-cysteine (Cys), tranexamic acid (Tranex) is reported. Speciation models have been obtained by processing potentiometric titration data to determine stability constants of the species formed in aqueous solution at T=298.15K, 0.15≤I/molL-1≤1 in NaCl. Thermodynamic formation parameters have been obtained from calorimetric titration data, at T=298.15K, I=0.15molL-1 using NaCl as ionic medium. Al3+-Cys system was also investigated by spectrophotometric and 1H NMR measurements. 1H NMR experiments were performed on Al3+-Tranex system as well. Different speciation models have been observed for the three systems. The results showed the formation of MLH, ML and M2L2(OH)2 species for Gly, ML, M2L and MLOH for Cys, MLH and MLOH for Tranex. The formed species are quite stable, i.e. for ML, logß=7.18, 11.91 for Gly and Cys, respectively, at I=0.15molL-1 and T=298.15K. For all the systems the dependence of formation constants on ionic strength over the range 0.1-1molL-1 is reported. The sequestering ability of the ligands under study was also evaluated by pL0.5 empiric parameter. For Gly, Cys and Tranex, pL0.5=2.51, 3.74, 3.91 respectively, at pH=5, I=0.15molL-1 and T=298.15K.