Emulsifying properties of sugar-based surfactants prepared by chemoenzymatic synthesis

Sugar Fatty Acid Esters (SFAEs) are a class of non-ionic surfactants that can be synthesized from inexpensive natural resources. Depending on carbon chain length and nature of the sugar head group, SFAEs cover a wide range of hydrophilic–lipophilic balance (HLB) values, which result in tunable tenside properties and in turn relevant for a wide variety of industrial applications. Three sugar-based surfactants (6-O-lauroyl-, 6-O-palmitoyl- and 6-O-stearoyl-1-O-butyl glucopyranosides) have been prepared by a lipase-catalyzed esterification of isomeric mixture of n-butyl glucosides. Specifically, their interfacial features together with W/O emulsifying properties and stability over time have been finely evaluated (interfacial tension (IFT) values, W/O emulsion turbidity water droplet size distribution, first order kinetic constants of de-emulsification)

Synergistic Effects of Active Sites' Nature and Hydrophilicity on Oxygen Reduction Reaction Activity of Pt-Free Catalysts

This work highlights the importance of the hydrophilicity of a catalyst’s active sites on an oxygen reduction reaction (ORR) through an electrochemical and physico-chemical study on catalysts based on nitrogen-modified carbon doped with different metals (Fe, Cu, and a mixture of them). BET, X-ray Powder Diffraction (XRPD), micro-Raman, X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM), Scanning Transmission Electron Microscopy (STEM), and hydrophilicity measurements were performed. All synthesized catalysts are characterized not only by a porous structure, with the porosity distribution centered in the mesoporosity range, but also by the presence of carbon nanostructures. In iron-doped materials, these nanostructures are bamboo-like structures typical of nitrogen carbon nanotubes, which are better organized, in a larger amount, and longer than those in the copper-doped material. Electrochemical ORR results highlight that the presence of iron and nitrogen carbon nanotubes is beneficial to the electroactivity of these materials, but also that the hydrophilicity of the active site is an important parameter affecting electrocatalytic properties. The most active material contains a mixture of Fe and Cu

Disclosing the Sensitivity and Selectivity of Metal Oxide/Graphene Oxide-Based Chemoresistors towards VOCs

Nowadays, gas sensors play a vital role in a plethora of applications. However, there are still some important shortcomings, such as the scarce selectivity and sensitivity, especially at low operating temperatures. Herein, we report the successful sensing achieved by tailoring the chemoresistive materials comprised of graphene oxide (GO) sheets well-integrated in a three-dimensional network of n-type metal oxide semiconductors (MOS). Thanks to the synergistic effect between GO and MOS under UV light, we obtained a very good sensitivity (down to 100 ppb) towards different volatile organic compounds (VOCs, i.e., ethanol, acetone, ethylbenzene, toluene) even at room temperature. Moreover, the best performing sensor (SnO2/GO 32:1) resulted in being highly selective towards polar compounds, such as acetone

Stable Coloured Micrometric Films from Highly Concentrated Nano-Silver Sols: The Role of the Stabilizing Agents

The synthesis of highly concentrated aqueous silver nanoparticles (NPs), exploiting different types of polymeric stabilizing agents, has been extensively investigated, especially for the stabilization of spherical yellow nanoparticles. In this context, here, a successful and easy wet chemical method was adopted to synthesize concentrated primary colored (yellow, red, blue and green) sols. The influence of polyvinylpyrrolidone (PVP) and polyvinyl alcohol (PVA) in affecting the final stability was finely investigating via UV/Vis spectroscopy, dynamic light scattering, TEM and colorimetric analysis. The next step consisted on the deposition of obtained sols onto a crown-treated polyethylene terephthalate (PET) support to obtain transparent colored micrometric homogeneous films. The fabricated PVP-based Ag films were revealed to be outstandingly UV-stable, contrarily to PVA-based films, probably due to the degradation of the polymer itself. Indeed, after UV aging tests, the PVA macromolecules could be broken and chemically modified (demonstrated by FT-IR analyses). This resulted in there being insufficient macromolecules to efficiently cover the surface of the nanoparticles, meaning that the nanoparticles tended to aggregate with each other, destabilizing the system itself. Hence, the obtained colored films described herein could represent a promising tool for different applications, from color shifting to optoelectronic devices

Enhanced Historical Limestone Protection by New Organic/Inorganic Additive-Modified Resins

The Cultural Heritage deterioration is a spontaneous decay process due to water percolation and air pollutant deposition. In this context, novel acrylic (Twinswet, TW) and siloxane-based (Alpha®SI30) resins were exploited starting from commercial products and then modified by adding either a commercial polysiloxane-based additive (TegoPhobe 1500N) or a precursor of SiO2 nanoparticles (Tetraethyl ortosilicate, TEOS) to improve the Vicenza stone surface hydrophobicity. Properties of the coated materials were studied using different techniques such as water contact angle (WCA), capillary absorption, colorimetric and water vapor permeability measurements. Accelerated UV aging and eight-month outdoor exposure tests (at Milan University campus) were also performed to determine the coatings durability. Notably, the addition of both additives slightly enhanced the surface hydrophobicity resulting in WCAs of about 140°, and decreased the water absorption especially for Alpha-based resins. Conversely, a reduction of water vapor permeability was observed, even if within the threshold value of 50%. Concerning the color variation, Alpha®SI30 preserved the stone external aspect; instead, TW smoothly modified the surface color. All of the studied coatings were stable to both UV aging and outdoor exposure. Hence, the present modified commercial coatings revealed to be very promising for the protection of historical monuments

Insight into the release agents/PVD coatings interaction for plastic mold technology

In polymer processing, the formation of undesired fouling hinders the plastic manufacturing processes. Hence, the use of emulsions as releasing agents is mandatory and their affinity to the mold substrates plays a crucial role. Therefore, this research work has been focused on the wetting properties of commercial water-based release agents (namely Marbocote® W2140, EP, EV-333) towards different Physical Vapor Deposition (PVD) nitride coatings (AlTiN, NbN, ZrN and TiN), usually adopted in the industrial manufacture of Hydrogenated Nitrile Butadiene Rubber (HNBR). The investigated solid substrates were characterized by means of profilometry, SEM/EDX and Surface Free Energy (SFE) analyses, whereas, tensiometric determinations were acquired on the commercial pure and diluted emulsions. The release agents/mold substrates wettability features were studied by means of the work of adhesion and the spreading coefficient. Finally, nitride-coated mold seals were directly tested in an industrial plant with the most performing release agent in terms of adhesive features; for the first time, a deep correlation between the service life, in terms of number of molded seals, and surface (contact angles, work of adhesion and spreading coefficient)/electrochemical (OCP) features was drawn

Acetone and Toluene Gas Sensing by WO3: Focusing on the Selectivity from First Principle Calculations

Sensitivity and selectivity are the two major parameters that should be optimized in chemiresistive devices with boosted performances towards Volatile Organic Compounds (VOCs). Notwithstanding a plethora of metal oxides/VOCs combinations that have been investigated so far, a close inspection based on theoretical models to provide guidelines to enhance sensors features has been scarcely explored. In this work, we measured experimentally the sensor response of a WO3 chemiresistor towards gaseous acetone and toluene, observing a two orders of magnitude higher signal for the former. In order to gain insight on the observed selectivity, Density Functional Theory was then adopted to elucidate how acetone and toluene molecules adsorption may perturb the electronic structure of WO3 due to electrostatic interactions with the surface and hybridization with its electronic structure. The results of acetone adsorption suggest the activation of the carbonyl group for reactions, while an overall lower charge redistribution on the surface and the molecule was observed for toluene. This, combined with acetone’s higher binding energy, justifies the difference in the final responses. Notably, the presence of surface oxygen vacancies, characterizing the nanostructure of the oxide, influences the sensing performances

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

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