Search

[Display omitted] Achieving a controlled preparation of nanoparticle superstructures with spatially periodic arrangement, also called superlattices, is one of the most intriguing and open questions in soft matter science. The interest in such regular superlattices originates from the potentialities in tailoring the physicochemical properties of the individual constituent nanoparticles, eventually leading to emerging behaviors and/or functionalities that are not exhibited by the initial building blocks. Despite progress, it is currently difficult to obtain such ordered structures; the influence of parameters, such as size, softness, interaction potentials, and entropy, are neither fully understood yet and not sufficiently studied for 3D systems. In this work, we describe the synthesis and characterization of spatially ordered hierarchical structures of coated cerium oxide nanoparticles in water suspension prepared by a bottom-up approach. Covering the CeO 2 surface with amphiphilic molecules having chains of appropriate length makes it possible to form ordered structures in which the particles occupy well-defined positions. In the present case superlattice arrangement is accompanied by an improvement in photoluminescence (PL) efficiency, as an increase in PL intensity of the superlattice structure of up to 400 % compared with that of randomly dispersed nanoparticles was observed. To the best of our knowledge, this is one of the first works in the literature in which the coexistence of 3D structures in solution, such as face-centered cubic (FCC) and Frank-Kasper (FK) phases, of semiconductor nanoparticles have been related to their optical properties. [ABSTRACT FROM AUTHOR]

Rhamnolipids represent a promising class of biosurfactants, whose industrial exploitation could potentially reduce the ecological impact of surfactant-based formulations. In this direction, the rational design of rhamnolipid mixtures with other surfactants constitutes a strategic field of research. In this work, we combine mono-rhamnolipid (mRha) with the cationic surfactant cetyltrimethylammonium chloride (CTAC). The study is conducted at pH = 7.1, so that the mRha carboxylic group is dissociated and catanionic mRha-CTAC mixtures form. The system is investigated across the entire composition range by surface tension and conductivity measurements, which show a strong synergism between the two surfactants in forming mixed aggregates, specifically in mRha-rich mixtures. No coacervation or precipitation is observed, due to the strong asymmetry between the surfactant molecular architectures, with mRha presenting a bulky headgroup and two relatively short tails compared to the single long tail of CTAC. Dynamic Light Scattering (DLS) and Small Angle Neutron Scattering (SANS) experiments show that, while the single surfactants predominantly form small micelles, their mixing results in the spontaneous formation of vesicles. Within the vesicle bilayer, the termini of the longer surfactant tails fold, assuming disordered conformations, as probed by Electron Paramagnetic Resonance (EPR) measurements. These results point to the rational design of rhamnolipid-based catanionic mixtures as a suitable tool to optimize their structural properties, constituting a solid basis for their practical applications. [Display omitted] • Monorhamnolipids (mRha) and CTAC co-aggregate forming catanionic aggregates. • mRha-CTAC mixed aggregation is synergistic, resulting in low cmc values. • At high mRha content, the mixture behavior is well described by the regular solution model. • mRha-CTAC aggregates present a vesicular structure. • In mixed bilayers the long CTAC tails fold, assuming disordered conformations. [ABSTRACT FROM AUTHOR]

This review provides an overview of experimental and computational results on the interaction between nanocarriers of different natures and pulmonary surfactant models that have appeared in the literature in the last five years. The purpose is to highlight the changes in the nanoscopic structure and functionality of the pulmonary surfactant layer due to the interaction with nanocarriers and nanoparticles, which are inorganic, polymeric, or consist of biomolecules. The information gathered contributes to the development of carriers' nanotechnology, thus allowing specific and controlled drug delivery while being minimally invasive by crossing pulmonary surfactant without altering its structure and function. [Display omitted] [ABSTRACT FROM AUTHOR]

The search for new synthetic melanin-related pigments that maintain the antioxidant and photoprotective properties of naturally occurring dark eumelanins, while overcoming their unfavorable solubility, and molecular heterogeneity is presently a very active issue for dermo-cosmetic purposes. In this work, we explored the potential of a melanin obtained from the carboxybutanamide of a major eumelanin biosynthetic precursor, 5,6-dihydroxyindole-2-carboxylic acid (DHICA), by aerobic oxidation under slightly alkaline conditions. Analysis of the pigment by EPR, ATR-FTIR and MALDI MS indicated a substantial structural similarity to DHICA melanin, while investigation of the early intermediates confirmed unchanged regiochemistry of the oxidative coupling. The pigment exhibited a UVA–visible absorption even more intense than that of DHICA melanin, and a noticeable solubility in polar solvents of dermo-cosmetic relevance. The hydrogen- and/or electron-donor ability, and the iron (III) reducing power as determined by conventional assays provided evidence for marked antioxidant properties not merely ascribable to the more favorable solubility profile, while the inhibitory action of the radical- or photosensitized solar light-induced lipid peroxidation was more marked compared to that of DHICA melanin. Overall, these results hint at this melanin, which remarkable properties are, in part, due to the electronic effects of the carboxyamide functionality as a promising functional ingredient for dermo-cosmetic formulations. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

[Display omitted] Halloysite nanotubes (HNTs) represent a versatile core structure for the design of functional nanosystems of biomedical interest. However, the development of selective methodologies for the site-controlled functionalization of the nanotubes at specific sites is not an easy task. This study aims to accomplish a procedure for the site-selective/specific, "pin-point", functionalization of HNTs with polydopamine (HNTs@PDA). This goal was achieved, at pH 6.5, by exploiting the basicity of ZnO nanoparticles anchored on the HNTs external surface (HNTs@ZnO) to induce a punctual polydopamine polymerization and coating. The morphology and the chemical composition of the nanomaterial was demonstrated by several techniques. Turbidimetric analysis showed that PDA coating affected the aqueous stability of HNTs@PDA compared to both HNTs@ZnO and HNTs. Notably, hyperthermia studies revealed that the nanomaterial induced a local thermic rise, up to 50 °C, under near-infrared (NIR) irradiation. Furthermore, secondary functionalization of HNTs@PDA by selective grafting of biotin onto the PDA coating followed by avidin binding was also accomplished. [ABSTRACT FROM AUTHOR]

This work studies the interaction of organic nanoparticles (ON) with various dyes in aqueous solution, to elucidate the role of ON on transport and fate of dyes in the environment, and on dyes removal from wastewater. Studied dyes are Acid Red 66 (AR66), Methylene Blue (MB), Reactive Black 5 (RB5), and Reactive Violet 5 (RV5). ON are extracted from organic matter of anthropogenic origin through resuspension of its colloidal fraction, and successive filtration and dialysis of the obtained suspension. Mechanisms of interaction are investigated initially through three-dimensional excitation emission matrix (3DEEM) analysis. Obtained data indicate that dynamic interactions occur strongly between dye molecules and ON aggregates. 3DEEM spectra of mixed samples containing ON together with one of the tested dyes, present a shape similar to the one of ON alone, but each of them is characterized by specific differences in terms of peaks quenching and shift. The analysis of these singularities suggests that dye molecules are bound to the functional groups of ON through H-bonds, according to the following steps: i) dyes reach the surface of ON aggregates; ii) the molecules pass through the hydrophilic surface of ON aggregates, and reach their hydrophobic core; iii) the dyes are sequestrated into the hydrophobic core of ON aggregates. Nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) spectroscopies analysis confirm the formation of supramolecular aggregates with stable micellar hydrophobic structure, mainly consisting of aliphatic fractions of ON, which explain the disappearance of aromatic groups signals from dyes. [Display omitted] • Interactions of organic nanoparticles (ON) with various dyes occurred strongly. • The disappearance of 3DEEM and NMR dye signals was discovered after interaction. • Hydrophobic core formed by aliphatic groups on ON sequestered aromatic dye molecules. • NMR and EPR analysis confirmed the formation of supramolecular aggregate of ON. [ABSTRACT FROM AUTHOR]