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Soluplus® is one of the most widely used amphiphilic copolymers in drug delivery and has been reported to strongly enhance the adsorption of model drugs. However, there is still a limited understanding of its micellar behavior as it responds to the different routes of administration, which involve important changes in concentration.The microstructure of Soluplus aqueous solutions has been investigated at a wide range of polymer concentrations (2 × 10We demonstrate the presence at all tested concentrations of two forms of Soluplus, with hydrodynamic radii of 3 and 26 nm, where the fraction of smaller objects accounts for as much as 60-70%. dNMR, SAXS, DLS and SLS indicate that Soluplus spontaneously self-assembles into large spherical particles with a core-shell structure. However, self-assembly takes place three orders of magnitude above the cmc evaluated via surface tension measurements. Instead of the traditional cooperative micellization process, we propose a thermal-activated isodesmic self-assembly of the small aggregates into core-shell micelles.

The high volatility, water‐immiscibility, and light/oxygen‐sensitivity of most aroma compounds represent a challenge to their incorporation in liquid consumer products. Current encapsulation methods entail the use of petroleum‐based materials, initiators, and crosslinkers as well as mixing, heating, and purification steps. Hence, more efficient and eco‐friendly approaches to encapsulation must be sought. Herein, we propose a simple method by making use of a pre‐formed amphiphilic polymer and employing the Hansen Solubility Parameters approach to determine which fragrances could be encapsulated by spontaneous coacervation in water. The coacervates do not precipitate as solids but they remain suspended as colloidally stable liquid microcapsules, as demonstrated by fluorescence correlation spectroscopy. The effective encapsulation of fragrance is proven through confocal Raman spectroscopy, while the structure of the capsules is investigated by means of cryo FIB/SEM, confocal laser scanning microscopy, and small‐angle X‐ray scattering., The use of a PEG‐g‐PVAc amphiphilic graft copolymer together with hydrophobic fragrances in aqueous medium leads to the spontaneous formation of colloidally stable suspensions of liquid coacervate droplets. Arrows indicate the local turbulences sustaining the spontaneous mixing of the components. The bottom panel shows the confocal Raman microspectroscopy mapping of a multicompartment coacervate droplet with carvone as fragrance.

Antonio Alessio Leonardi,1– 3 Rosalia Battaglia,4 Dario Morganti,1,2 Maria Josè Lo Faro,1,3 Barbara Fazio,2 Chiara De Pascali,5 Luca Francioso,5 Gerardo Palazzo,6,7 Antonia Mallardi,8 Michele Purrello,4 Francesco Priolo,1 Paolo Musumeci,1,* Cinzia Di Pietro,4,* Alessia Irrera2,* 1Dipartimento di Fisica e Astronomia, Università di Catania, Catania, 95123, Italy; 2CNR-IPCF, Istituto per i Processi Chimico-Fisici, Messina, 98158, Italy; 3CNR-IMM UoS Catania, Istituto per la Microelettronica e Microsistemi, Catania, 95123, Italy; 4Department of Biomedical and Biotechnological Sciences, University of Catania, Catania, Italy; 5CNR-IMM, Institute for Microelectronics and Microsystems, Via Monteroni, University Campus, Lecce, 73100, Italy; 6Chemistry Department, University of Bari ‘Aldo Moro’, Bari, 70125, Italy; 7CSGI, Center for Colloid and Surface Science c/o Chemistry Department, Bari, 70125, Italy; 8CNR-IPCF, Institute for Chemical-Physical Processes, c/o Chemistry Department, Bari, 70125, Italy*These authors contributed equally to this workCorrespondence: Paolo Musumeci; Cinzia Di Pietro Email paolo.musumeci@ct.infn.it; dipietro@unict.itIntroduction: Small extracellular vesicles (sEVs), thanks to their cargo, are involved in cellular communication and play important roles in cell proliferation, growth, differentiation, apoptosis, stemness and embryo development. Their contribution to human pathology has been widely demonstrated and they are emerging as strategic biomarkers of cancer, neurodegenerative and cardiovascular diseases, and as potential targets for therapeutic intervention. However, the use of sEVs for medical applications is still limited due to the selectivity and sensitivity limits of the commonly applied approaches.Methods: Novel sensing solutions based on nanomaterials are arising as strategic tools able to surpass traditional sensor limits. Among these, Si nanowires (Si NWs), realized with cost-effective industrially compatible metal-assisted chemical etching, are perfect candidates for sEV detection.Results: In this paper, the realization of a selective sensor able to isolate, concentrate and quantify specific vesicle populations, from minimal volumes of biofluid, is presented. In particular, this Si NW platform has a detection limit of about 2× 105 sEVs/mL and was tested with follicular fluid and blastocoel samples. Moreover, the possibility to detach the selectively isolated sEVs allowing further analyses with other approaches was demonstrated by SEM analysis and several PCRs performed on the RNA content of the detached sEVs.Discussion: This platform overcomes the limit of detection of traditional methods and, most importantly, preserves the biological content of sEVs, opening the route toward a reliable liquid biopsy analysis.Keywords: silicon nanowires, biosensor, small extracellular vesicles, label-free, luminescence

The interactions between diluted phospholipid vesicles (0.3 μM - 40 μM) and surfactants (around their cmc) have been investigated as model of the phenomena taking place when enveloped viruses are challenged by detergent formulations such as mouthwashes or dishwashing liquids. We have used negatively charged Small Unilamellar Vesicles (SUVs) to simulate the negatively charged viral envelope and surfactants with different charges: the anionic Sodium Dodecyl Sulphate (SDS), the cationic Cetylpyridinium Chloride (CPC) and the non-ionic Octaethylene glycol monodecyl ether (C

This is an introductory review on the diffusion Nuclear Magnetic Resonance (dNMR) as a powerful tool to characterise different types of formulations. Such a technique is nowadays available on most of the NMR instrumentation and enables the determination of the distribution of components and the microstructure of the system. We start with a description, addressed to the formulators, of the methodological strategies to be used to determine the microstructure of different systems. The approaches to be used to quantify the partition/binding equilibria are then sketched. Then, we review recent dNMR applications to formulations containing ionic liquids, surfactants, polymers, and gels.

Mussel-forming fibers manifest fascinating properties due to the numerous reactive functional groups present in their primary structure besides their secondary structures. Humans adopted these protein-based fibers to produce an extremely fine and valuable fabric, named byssus. Byssus is the bundle of filaments secreted by Pinna nobilis species employed to colonize the marine substrates. The byssus fibers coming from other species, such as Mytilus edulis, have been widely investigated in particular for their self-healing properties attributed to the collagen presence and their core-shell structure. Surprisingly, the Pinna nobilis byssus is non-collagenous based and the fibers nanostructure is still poorly understood. Here, we are reporting an investigation on the Pinna nobilis byssus samples retrieved intact in each stage of treatment. The scanning electron microscope (SEM) provides a peculiar feature of Pinna nobilis byssus, i.e. the elliptical cross-section of the fibers. Wide-angle X-ray scattering (WAXS), as well as infrared spectroscopy (IR), reveal the presence of hydroxyapatite adsorbed at the surface of the initial fibers and the presence of crystalline beta-sheet domains within the fibers. Finally, a WAXS-based method reveals a decrease in the crystalline/amorphous ratio during byssus treatment.

In this work Nanoparticle Enhanced Laser Induced Breakdown Spectroscopy (NELIBS) has been employed for quantitative metal detection using amyloid fibrils coated with gold nanoparticles as enhancers. Amyloid fibrils represent, from one hand, an extremely interesting system for novel technologies, ranging from water purification to medical applications, and on the other hand, an ideal system for investigating the performance of laser-matter interaction in biological systems. The results obtained in this work show the potentiality of NELIBS for the quantification at sub-ppm (mg/kg) level of metallic elements (Cr, Pb, Tl and Cd) even in the protein and/or biological environment, employing amyloid fibrils with gold nanoparticles. Moreover, the single-shot measurements reveal the promising use of this technique in applications where high sensitivity and/or limitation in the sample amount are demanded.

In this work we demonstrated that the peripherical thioacetylation of a bithiophene-DPP molecule can greatly influence the solid-state properties triggering the formation of NIR emitting

Gold nanoparticles (AuNPs), synthesized by ns-pulsed laser ablation in liquid (ns-PLAL) in the absence of any capping agents, are potential model systems to study the interactions with biological structures unencumbered by interference from the presence of stabilizers and capping agents. However, several aspects of the physics behind these AuNPs solutions deserve a detailed investigation. The structure in solution of ns-PLAL-synthesized AuNPs was investigated in solution by means of small-angle X-ray scattering (SAXS) and dynamic light scattering (DLS). Furthermore, the (dried) NPs have been examined using TEM. The analysis of the SAXS curve shows the presence of a large number of small aggregates with a fractal structure stabilized by strong long-range repulsive interactions. Fitting of the SAXS curve to a suitable “fractal model” allows the estimation of the features of the fractal including the fractal dimension d = 1.9. The latter allows to estimate the fraction of light scattered by fractals of different sizes and thus permits a fair comparison between the DLS and TEM data. Here, a stable abundant population of fractal clusters is reported reflecting a mechanism where primary AuNPs (size 7.6 nm) are forced to aggregate forming clusters during the collapse of the cavitation bubble. When these clusters are released in the aqueous phase, their large negative charge builds up repulsive interactions that prevent cluster-cluster aggregation imparting colloidal stability.

Transmission of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) can occur through saliva and aerosol droplets deriving from the upper aerodigestive tract during coughing, sneezing, talking, and even during oral inspection or dental procedures. The aim of this study was to assess in vitro virucidal activity of commercial and experimental mouthwashes against a feline coronavirus (FCoV) strain. Commercial and experimental (commercial-based products with addition of either sodium dodecyl sulfate (SDS) or thymus vulgaris essential oil (TEO) at different concentrations) mouthwashes were placed in contact with FCoV for different time intervals, that is, 30s (T30), 60s (T60), and 180s (T180); subsequently, the virus was titrated on Crandell Reese Feline Kidney cells. An SDS-based commercial mouthwash reduced the viral load by 5log10 tissue culture infectious dose (TCID)50/50µl at T30 while a cetylpyridinium (CPC)-based commercial mouthwash was able to reduce the viral titer of 4.75log10 at T60. Furthermore, five experimental mouthwashes supplemented with SDS reduced the viral titer by 4.75–5log10 according to a dose- (up to 4mM) and time-dependent fashion.

Xylella fastidiosa is among the most dangerous plant bacteria worldwide causing a variety of diseases, with huge economic impact on agriculture and environment. A surveillance tool, ensuring the highest possible sensitivity enabling the early detection of X. fastidiosa outbreaks, would be of paramount importance. So far, a variety of plant pathogen biomarkers are studied by means of surface plasmon resonance (SPR). Herein, multiparameter SPR (MP‐SPR) is used for the first time to develop a reliable and label‐free detection method for X. fastidiosa. The real‐time monitoring of the bioaffinity reactions is provided as well. Selectivity is guaranteed by biofunctionalizing the gold transducing interface with polyclonal antibodies for X. fastidiosa and it is assessed by means of a negative control experiment involving the nonbinding Paraburkholderia phytofirmans bacterium strain PsJN. Limit of detection of 105 CFU mL−1 is achieved by transducing the direct interaction between the bacterium and its affinity antibody. Moreover, the binding affinity between polyclonal antibodies and X. fastidiosa bacteria is also evaluated, returning an affinity constant of 3.5 × 107 m−1, comparable with those given in the literature for bacteria detection against affinity antibodies.

Metal nanoparticles (NPs) made of gold, silver, and platinum have been synthesized by means of pulsed laser ablation in liquid aqueous solution. Independently from the metal nature, all NPs have an average diameter of 10 &plusmn, 5 nm. The &zeta, potential values are: &minus, 62 &plusmn, 7 mV for gold, &minus, 44 &plusmn, 2 mV for silver and &minus, 58 &plusmn, 3 for platinum. XPS analysis demonstrates the absence of metal oxides in the case of gold and silver NPs. In the case of platinum NPs, 22% of the particle surface is ascribed to platinum oxidized species. This points to a marginal role of the metal oxides in building the negative charge that stabilizes these colloidal suspensions. The investigation of the colloidal stability of gold NPs in the presence of metal cations shows these NPs can be destabilized by trace amounts of selected metal ions. The case of Ag+ is paradigmatic since it is able to reduce the NP &zeta, potential and to induce coagulation at concentrations as low as 3 &mu, M, while in the case of K+ the critical coagulation concentration is around 8 mM. It is proposed that such a huge difference in destabilization power between monovalent cations can be accounted for by the difference in the reduction potential.

The direct interaction of atmospheric pressure non-equilibrium plasmas with tyrosinase (Tyr) was investigated under typical conditions used in surface processing. Specifically, Tyr dry deposits were exposed to dielectric barrier discharges (DBDs) fed with helium, helium/oxygen, and helium/ethylene mixtures, and effects on enzyme functionality were evaluated. First of all, results show that DBDs have a measurable impact on Tyr only when experiments were carried out using very low enzyme amounts. An appreciable decrease in Tyr activity was observed upon exposure to oxygen-containing DBD. Nevertheless, the combined use of X-ray photoelectron spectroscopy and white-light vertical scanning interferometry revealed that, in this reactive environment, Tyr deposits displayed remarkable etching resistance, reasonably conferred by plasma-induced changes in their surface chemical composition as well as by their coffee-ring structure. Ethylene-containing DBDs were used to coat tyrosinase with a hydrocarbon polymer film, in order to obtain its immobilization. In particular, it was found that Tyr activity can be fully retained by properly adjusting thin film deposition conditions. All these findings enlighten a high stability of dry enzymes in various plasma environments and open new opportunities for the use of atmospheric pressure non-equilibrium plasmas in enzyme immobilization strategies.

Gold nanoparticles (AuNPs) were produced using stainless steel as a solid reductant to assist the synthesis of metal NPs, using HAuCl4 as a precursor. This method is very easy, quick, and cost-effective, allowing the synthesis of highly stable NPs without additional capping agents. However, the reaction mechanism is still under debate. In order to contribute to the investigation of the synthesis of AuNPs using stainless steel, different experimental conditions were tested. Cl&minus, concentration, pH of the precursor solution, as well as stainless steel composition were systematically changed. The syntheses were performed recording the open circuit potential to potentiometrically explore the electrochemical properties of the system, under operando conditions. Spectroscopic and morphological characterizations were carried out along with potentiometric monitoring, aiming at correlating the synthesis parameters with the AuNPs characteristics. As a result, an overview of the process features, and of its most reasonable mechanism were obtained.

Zinc oxide (ZnO) nanostructures are widely applied materials, and are also capable of antimicrobial action. They can be obtained by several methods, which include physical and chemical approaches. Considering the recent rise of green and low-cost synthetic routes for nanomaterial development, electrochemical techniques represent a valid alternative to biogenic synthesis. Following a hybrid electrochemical-thermal method modified by our group, here we report on the aqueous electrosynthesis of ZnO nanomaterials based on the use of alternative stabilizers. We tested both benzyl-hexadecyl-dimetylammonium chloride (BAC) and poly-diallyl-(dimethylammonium) chloride (PDDA). Transmission electron microscopy images showed the formation of rod-like and flower-like structures with a variable aspect-ratio. The combination of UV&ndash, Vis, FTIR and XPS spectroscopies allowed for the univocal assessment of the material composition as a function of different thermal treatments. In fact, the latter guaranteed the complete conversion of the as-prepared colloidal materials into stoichiometric ZnO species without excessive morphological modification. The antimicrobial efficacy of both materials was tested against Bacillus subtilis as a Gram-positive model microorganism.

Microemulsions are thermodynamically stable, transparent, isotropic single-phase mixtures of two immiscible liquids stabilized by surfactants (and possibly other compounds). The assortment of very different microstructures behind such a univocal macroscopic definition is presented together with the experimental approaches to their determination. This tutorial review includes a necessary overview of the microemulsion phase behavior including the effect of temperature and salinity and of the features of living polymerlike micelles and living networks. Once these key learning points have been acquired, the different theoretical models proposed to rationalize the microemulsion microstructures are reviewed. The focus is on the use of these models as a rationale for the formulation of microemulsions with suitable features. Finally, current achievements and challenges of the use of microemulsions are reviewed.

Cardiovascular diseases are some of the today major cause of death in the world. C-reactive protein (CRP) is well known as the main biomarker related to cardiovascular risk and heart attack occurrence. The standard CRP analyses are performed in a hospital or in a biochemical laboratory with blood analysis after a long chemical and labelling preparation that require expert personnel. In this scenario, a health care analysis that can be performed by the same patient at his own home appears extremely revolutionary. In this paper, the study of an innovative sensing platform based on the luminescence at room temperature of silicon nanowires (NWs) is reported. This NWs sensor is label-free and does not require a chemical treatment of the analyte, is strongly selective to the CRP demonstrating a femtomolar limit of detection and a wide operating range. This proposed silicon sensing platform can be realized with an industrial compatible approach and permits to reveal the strategic CRP level in saliva in order to prevent a heart attack, with great advantages for the patient.

Protein-surfactant interactions are the focus of extensive research due to their many applications in food technology and detergent industry. In this work, we investigate the interaction between bovine serum albumin (BSA) and five relevant surfactants to the cleaning industry, which differ in head group charge, namely: sodium alkyl ether sulphate (C12-C14 AE3S), Cocoamidopropyl amine-oxide (CapAO), alkyl dimethyl amine oxide (C12C14AO), octaethylene glycol monodecyl ether (C10EO8) and didecyldimethylammonium chloride (DDAC). The results collected with fluorescence emission spectroscopy highlight zwitterionic and nonionic surfactants have the lowest affinity for the protein, as their interaction does not result in protein denaturation. Instead, higher and mutually close binding constants are found for AE3S (anionic) and DDAC (cationic) due to the presence of electrostatic interactions between the surfactant heads and the charged residues of BSA. AE3S leads to irreversible protein unfolding. The case of DDAC is more complex and has been studied through a combination of fluorescence, DLS, PGSE-NMR and zeta-potential measurements. At low concentration DDAC binding neutralizes negatively charged residues present in BSA, causing a reversible flocculation of BSA after the isoelectric point (23 DDAC molecules per protein). Further DDAC adsorption, at 70 DDAC molecules per protein, leads to an excess of positive charge on the protein which restores electrostatic repulsions between BSA-surfactant complexes.