Calcitic-based stones protection by a low-fluorine modified methacrylic coating.

Atmospheric pollutants, such as NOx, SO2, and particulate matter, together with water percolation inside the stone pores, represent the main causes of cultural heritage decay. In order to avoid these undesired phenomena, the application of protective coatings represents a reliable solution. In this context, the present study focused on the synthesis of low-fluorine content methacrylic-based (MMA) polymeric resins characterized by seven F atoms (namely F7 monomer) in the lateral chains. Four different percentages (1.0, 2.5, 5.0, and 10.0%) of the present monomer were adopted to obtain a final polymeric structure showing the desired hydrophobicity, processability, and structural and thermal stability (even after accelerated UV aging tests). MMA_F7(1.0) seemed to be the optimal one; therefore, it was further applied onto Candoglia marble. Specifically, the treated substrates showed good surface hydrophobicity, water repellency, and water vapor transpirability. No color variation was observed even after a 1.5-year exposure in a real polluted environment (Monza Cathedral). Interestingly, the application of this coating hindered the atmospheric nitrates penetration inside the stones and, at the same time, it limited the sulfates (gypsum) formation, thus revealing a very promising marbles protection resin.

Design of New Polyacrylate Microcapsules to Modify the Water-Soluble Active Substances Release.

Despite the poor photochemical stability of capsules walls, polyacrylate is one of the most successful polymers for microencapsulation. To improve polyacrylate performance, the combined use of different acrylate-based polymers could be exploited. Herein butyl methacrylate (BUMA)-based lattices were obtained via free radical polymerization in water by adding (i) methacrylic acid (MA)/methyl methacrylate (MMA) and (ii) methacrylamide (MAC) respectively, as an aqueous phase in Pickering emulsions, thanks to both the excellent polymer shells' stability and the high encapsulation efficiency. A series of BUMA_MA_MMA terpolymers with complex macromolecular structures and BUMA_MAC linear copolymers were synthesized and used as dispersing media of an active material. Rate and yield of encapsulation, active substance adsorption onto the polymer wall, capsule morphology, shelf-life and controlled release were investigated. The effectiveness of the prepared BUMA-based microcapsules was demonstrated: BUMA-based terpolymers together with the modified ones (BUMA_MAC) led to slow (within ca. 60 h) and fast (in around 10 h) releasing microcapsules, respectively.

Nanostructured Oxide-Based Systems for the pH-Triggered Release of Cinnamaldehyde.

Cinnamaldehyde is a natural product with antibacterial, antifungal, and anti-inflammatory properties, poorly stable in environmental conditions. Systems for the controlled release of cinnamaldehyde are of great interest to the food and pharmaceutical industries. Here, a new oxide-based construct for the release of cinnamaldehyde catalyzed by acidic pH was obtained by a facile grafting method based on amino-silane linkers and imine chemistry. The grafting procedure led to a loading of ca. 5 molecules/nm2, determined on oxide powders with CHN and TGA measurements. The covalent grafting of cinnamaldehyde, demonstrated by FTIR analyses, preserved the molecule stability, simplifying storage. Release tests were performed at different pH values (between 5.0 and 7.4). Thanks to imine chemistry, a fast cinnamaldehyde (CIN) release was observed in a pH 5.0 environment. Using 1 mg/mL suspensions, CIN concentrations within the range adopted in the food industry were obtained (12.4 ppm). The grafting procedure was also performed on a porous film based on a photocatalytic oxide, demonstrating the versatility of this method, adaptable to both powders and macroscopic materials. By taking advantage of the photoactivity of the oxide, regeneration of the fouled film was achieved upon UV irradiation for 1 h, opening the door to reusable devices for the controlled release of cinnamaldehyde.

Role of Doping Agent Degree of Sulfonation and Casting Solvent on the Electrical Conductivity and Morphology of PEDOT:SPAES Thin Films.

Poly(3,4-ethylenedioxythiophene) (PEDOT) plays a key role in the field of electrically conducting materials, despite its poor solubility and processability. Various molecules and polymers carrying sulfonic groups can be used to enhance PEDOT's electrical conductivity. Among all, sulfonated polyarylether sulfone (SPAES), prepared via homogenous synthesis with controlled degree of sulfonation (DS), is a very promising PEDOT doping agent. In this work, PEDOT was synthesized via high-concentration solvent-based emulsion polymerization using 1% w/w of SPAES with different DS as dopant. It was found that the PEDOT:SPAESs obtained have improved solubility in the chosen reaction solvents, i.e., N, N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone and, for the first time, the role of doping agent, DS and polymerization solvents were investigated analyzing the electrical properties of SPAESs and PEDOT:SPAES samples and studying the different morphology of PEDOT-based thin films. High DS of SPAES, i.e., 2.4 meq R-SO3-× g-1 of polymer, proved crucial in enhancing PEDOT's electrical conductivity. Furthermore, the DMSO capability to favor PEDOT and SPAES chains rearrangement and interaction results in the formation of a polymer film with more homogenous morphology and higher conductivity than the ones prepared from DMAc, DMF, and NMP.

PA6 and Halloysite Nanotubes Composites with Improved Hydrothermal Ageing Resistance: Role of Filler Physicochemical Properties, Functionalization and Dispersion Technique.

Polyamide 6 (PA6) suffers from fast degradation in humid conditions due to hydrolysis of amide bonds, which limits its durability. The addition of nanotubular fillers represents a viable strategy for overcoming this issue, although the additive/polymer interface at high filler content can become privileged site for moisture accumulation. As a cost-effective and versatile material, halloysite nanotubes (HNT) were investigated to prepare PA6 nanocomposites with very low loadings (1-45% w/w). The roles of the physicochemical properties of two differently sourced HNT, of filler functionalization with (3-aminopropyl)triethoxysilane and of dispersion techniques (in situ polymerization vs. melt blending) were investigated. The aspect ratio (5 vs. 15) and surface charge (-31 vs. -59 mV) of the two HNT proved crucial in determining their distribution within the polymer matrix. In situ polymerization of functionalized HNT leads to enclosed and well-penetrated filler within the polymer matrix. PA6 nanocomposites crystal growth and nucleation type were studied according to Avrami theory, as well as the formation of different crystalline structures (α and γ forms). After 1680 h of ageing, functionalized HNT reduced the diffusion of water into polymer, lowering water uptake after 600 h up to 90%, increasing the materials durability also regarding molecular weights and rheological behavior.

Towards Novel Fluorinated Methacrylic Coatings for Cultural Heritage: A Combined Polymers and Surfaces Chemistry Study.

In this work, new co- and ter-polymers of methyl methacrylate (MMA), ethyl methacrylate (EMA), and N-butyl methacrylate (nBuMA), containing just 1% mol × mol-1 of a fluorinated co-monomer, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-octyl methacrylate (POMA), were synthesized. After an UV accelerated aging test, the photo-chemical stability of the polymers prepared was determined by 1H NMR and FT-IR spectroscopy, size exclusion chromatography, differential scanning calorimetry and wettability measurements. The polymers were applied to Botticino tiles to achieve better performances in terms of water repellency and consequently deterioration resistance. One-year prolonged exposure to a real environment was conducted and the properties of the coated materials and their performances were studied using different surface techniques such as water contact angle (WCA) and colorimetric measurements (CIELaB), capillary absorption, permeability (RVP) tests and soluble salts determination. The effectiveness of the fluorinated methacrylic coatings was clearly demonstrated; among all the resins, the co-polymer MMA_POMA seems to be the most performing one. Furthermore, both the UV photo-chemical resistance and the easiness of removal was successfully studied.

Polystyrene microplastics ingestion induced behavioral effects to the cladoceran Daphnia magna.

Microplastic (µPs) contamination represents a dramatic environmental problem threatening both aquatic and terrestrial organisms. Although several studies have highlighted the presence of µPs in aquatic environments, the information regarding their toxicity towards organisms is still scant. Moreover, most of the ecotoxicological studies of µPs have focused on marine organisms, largely neglecting the effects on freshwater species. The present study aimed at exploring the effects caused by 21-days exposure to three concentrations (0.125, 1.25 and 12.5 µg/mL) of two differently sized polystyrene microplastics (PµPs; 1 and 10 µm) to the Cladoceran Daphnia magna. The ingestion/egestion capability of daphnids (<24 h) and adults, the changes in individual growth and behavior, in terms of changes in swimming activity, phototactic behavior and reproduction, were investigated. Both particles filled the digestive tract of daphnids and adults within 24 h of exposure at all the tested concentrations. Ingested PµPs remained in the digestive tract even after 96 h in a clean medium. For both particles, an overall increase in body size of adults was noted at the end of the exposure to the highest tested concentrations, accompanied by a significant increase in swimming activity, in terms of distance moved and swimming velocity, and by an alteration of the phototactic behavior. A significant increase in the mean number of offspring after the exposure to the highest PµPs concentrations of different size was recorded. Polystyrene µPs can affect behavioral traits of D. magna leading to potentially harmful consequences on population dynamics of this zooplanktonic species.

Polyphenol Polymerization by an Alternative Oxidative Microbial Enzyme and Characterization of the Biological Activity of Oligomers.

The recombinant catalase-peroxidase HPI from E. coli was used as an alternative enzyme in polymerization reactions for the production of (-) epicatechin oligomers and their biological activity was characterized. The enzyme was prepared in two forms: a purified and an immobilized form. Both were tested for their activity in oxidative polymerization reactions, and their stability and reusability were assessed. The polymerization reactions were followed by SEC-HPLC analyses, and the substrate was completely converted into one or more polymerization products depending on the reactions conditions. Results showed that the utilized conditions allowed for the isolation of some oligomers of different molecular weight: the oligomers containing 6 and 7 units of epicatechin substrate are the heaviest ones. Epicatechin was also used in reactions catalyzed by HRP in the same reaction conditions for comparison. In addition, one selected oligomer obtained by HPI enzyme catalysis was shown to act as in vitro inhibitor of tumor cell growth, like one oligomer deriving from epicatechin by HRP catalysis. These data confirm that epicatechin oligomeric form is more effective than its monomer in biological activity and suggest the use of HPI as an alternative enzyme in reactions for the production of epicatechin oligomers.

A Combined XRD, Solvatochromic, and Cyclic Voltammetric Study of Poly (3,4-Ethylenedioxythiophene) Doped with Sulfonated Polyarylethersulfones: Towards New Conducting Polymers.

Despite the poor solubility in organic solvents, poly (3,4-ethylenedioxythiophene) (PEDOT) is one of the most successful conducting polymers. To improve PEDOT conductivity, the dopants commonly used are molecules/polymers carrying sulfonic functionalities. In addition to these species, sulfonated polyarylethersulfone (SPAES), obtained via homogeneous synthesis with different degrees of sulfonation (DS), can be used thanks to both the tight control over the DS and the charge separation present in SPAES structure. Here, PEDOTs having enhanced solubility in the chosen reaction solvents (N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone) were synthesized via a high-concentration solvent-based emulsion polymerization with very low amounts of SPAES as dopant (1% w/w with respect to EDOT monomer), characterized by different DS. The influence of solvents and of the adopted doping agent was studied on PEDOT_SPAESs analyzing (i) the chemical structure, comparing via X-ray diffraction (XRD) the crystalline structures of undoped and commercial PEDOTs with PEDOT_SPAES' amorphous structure; (ii) solvatochromic behavior, observing UV absorption wavelength variation as solvents and SPAES' DS change; and (iii) electrochemical properties: voltammetric peak heights of PEDOT_SPAES cast onto glassy carbon electrodes differ for each solvent and in general are better than the ones obtained for neat SPAES, PEDOTs, and glassy carbon.