In this work, a novel composite sorbent material for water remediation from oily contaminants, based on a cellulose three-dimensional fibrous scaffold treated with stearic acid and expanded graphite flakes, is presented. The pristine cellulose foams are inherently omniphilic, absorbing indiscriminately both water and oils. However, after being modified with stearic acid and graphite via drop casting, they become superhydrophobic (still preserving their superoleophilic characteristics). As a result, the foams start exhibiting a highly selective behaviour which permits to absorb different kinds of oils and organic solvents, while repelling water completely. Thermal and chemical characterizations reveal that the modification treatment is successfully performed, while the performed mechanical tests demonstrate a good recovery of elasticity after repeated deformations and confirm that the elasticity of the foam is preserved after the treatment. Although based on natural materials, the fabricated foams exhibit oil absorption rate, saturation time and capacity values comparable to those of some synthetic materials with the same aim, exhibiting a very important added value, as it is based on low cost, green and biodegradable materials, requiring, at the same time, low processing costs and providing excellent reusability properties.

Paramagnetic iron oxide nanoparticles have been synthetized and covered by a silica shell for a dual function: SiO2 capping improves the stability of the nanoparticles and at the same time promotes the bonding between the paramagnetic nanoparticles@SiO2 (MNPs@SiO2) and biogenic amines. The constituents of the paramagnetic nanoparticles have been identified to be magnetite and maghemite by Infrared and Raman spectroscopy; these optical investigations also allow confirmation of the key role of the capping layer in the interaction with the amines. The magnetic adducts with the biogenic amines can be removed simply and rapidly through the application of weak magnetic fields. The observation of the quickness and ease of biogenic amine elimination has prompted us to check the application of this new approach to real commercial wine samples containing these toxic fermentation products: their complete removal has been observed by absorption spectra, thus confirming the potential of this novel approach in agroindustrial areas and agribusiness.

Dietary phytochemicals found in vegetables and fruits consist of a wide variety of biologically active compounds with anti-carcinogenic activity. The aim of this study was to evaluate the antigrowth activity of carnosol, a dietary diterpene, as a single agent or in combination with other dietary phytochemicals or chemotherapeutic drugs against a panel of tumor cell lines. Carnosol decreased cell viability in human breast, ovarian, and intestinal tumor cell lines, and inhibited cancer cell adhesion on fibronectin and growth of cancer cells in suspension. Carnosol also inhibited EGF-induced epithelial mesenchymal transition in ovarian cancer cells. The combination treatment with other dietary phytochemicals increased the anti-proliferative activity of carnosol. The combination with curcumin resulted in a synergistic reduction of vitality in SKOV-3 and MDA-231 cells and potently inhibited viability of primary cancer cells isolated from the pleural fluid or ascites of patients with metastatic cancers. These results provide additional evidence about the anticancer role of carnosol and its potential in blocking the growth of tumor cells.

A porous collagen-based hydrogel scaffold was prepared in the presence of iron oxide nanoparticles (NPs) and was characterized by means of infrared spectroscopy and scanning electron microscopy. The hybrid scaffold was then loaded with fluorescein sodium salt as a model compound. The release of the hydrosoluble species was triggered and accurately controlled by the application of an external magnetic field, as monitored by fluorescence spectroscopy. The biocompatibility of the proposed matrix was also tested by the MTT assay performed on 3T3 cells. Cell viability was only slightly reduced when the cells were incubated in the presence of the collagen-NP hydrogel, compared to controls. The economicity of the chemical protocol used to obtain the paramagnetic scaffolds as well as their biocompatibility and the safety of the external trigger needed to induce the drug release suggest the proposed collagen paramagnetic matrices for a number of applications including tissue engeneering and drug delivery.

Cu, H2-bis-porphyrin (Cu, H2-Por2), in which copper porphyrin and free-base porphyrin are linked together by an ethano-bridge, was dissolved in chloroform and spread at the air/liquid subphase interface of a Langmuir trough. The bis-porphyrin derivative, floating film was characterized by reflection spectroscopy and the surface pressure of the floating film was studied as a function of the mean area per molecule. When aromatic amines are dissolved in the subphase, an evident interaction between the bis-porphyrin host and the aromatic amine guest is observed. A clear-cut variation of the profile of surface pressure vs area per molecule curve is observed. Reflection spectroscopy highlights that the aromatic amines dissolved in the subphase are able to induce the syn-to-anti conformational switching in the bis-porphyrin derivative. The Langmuir-Schaefer technique has been used to transfer the floating bisporphyrin film (when using pure water as a subphase) to a surface plasmon resonance (SPR) substrate and the resulting device was able to detect the presence of aniline at concentrations as low as 1 nM in aqueous solution. The high selectivity of the SPR sensing device has been verified by checking the spectral response of the active layer towards other analytes dissolved in the aqueous solutions.

The synthetic conjugated poly(1, 4-arylene-2, 5-thienylene) containing benzo[c][2,1,3]thiadiazole monomeric units (Bz-PAT) is proposed as active layer for the selective detection of mercuric ions. The Bz-PAT polymer chemical structure induces the formation of a disordered film with numerous vacancies and the size of these defects could be exploited for a reversible trapping of mercuric ions. For these reasons the Langmuir-Schaefer (LS) deposition method has been employed for transferring Bz-PAT layers with the desired accurate bi-dimensional organization control of the layer and with a high control of the deposition parameters. In this contribution, the frequency variation of a quartz crystal microbalance with 10, 20, 30 and 40 LS runs of Bz-PAT has been investigated in response to the injection of aqueous solutions of HgCl2, Pb(NO3)2, NiCl2, CdCl2 and ZnSO4 at different concentrations (0.5 mM, 1 mM, 5 mM). An almost linear dependence on the number of the LS layers and hence on the film thickness, measured by means of ellipsometric spectroscopy, has been found in terms of sensor response to concentration of Hg2+ ions fluxed. By means of UV-Vis spectroscopy, the variations in the -* absorption band of the polymer, attributed to the thiophene segment, induced by HgCl2 injection has been analyzed and explained as a consequence of the electron transfer from the mercuric ion to the polymer solid film. These results, together with the linear relation found between the number of deposited layers and LS film thickness, suggest that the sensing mechanism can be explained both by an electron interaction active layer and analyte and a diffusion mechanism of Hg2+ into the solid film that reaches an asymptotic value at 30 runs (about 80 nm), then a higher number of layers does not influence the sensor sensibility.

A totally green synthesis protocol has been adopted to obtain silver nanoaggregates capped by the natural compound (1E, 6E)-1,7-Bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5- diene), also known as curcumin. The synthesis process has been monitored by means of infrared, Raman, visible and fluorescence spectroscopies. Characterization confirms that curcumin reduces and caps the nanoparticles and such procedure allows its solubility in water and drastically increases the curcumin stability. Silver nanoparticles (AgNPs)/curcumin complex has been dispersed in a water solution containing a known nickel ion concentration. After three days a grey precipitate is observed and the nickel concentration in the solution is reduced of about 70%.

The aim of this work was to investigate the structural features of type I collagen isoforms and collagen-based films at atomic and molecular scales, in order to evaluate whether and to what extent different protocols of slurry synthesis may change the protein structure and the final properties of the developed scaffolds. Wide Angle X-ray Scattering data on raw materials demonstrated the preferential orientation of collagen molecules in equine tendon-derived collagens, while randomly oriented molecules were found in bovine skin collagens, together with a lower crystalline degree, analyzed by the assessment of FWHM (Full Width at Half Maximum), and a certain degree of salt contamination. WAXS and FT-IR (Fourier Transform Infrared) analyses on bovine collagen-based films, showed that mechanical homogenization of slurry in acidic solution was the treatment ensuring a high content of super-organization of collagen into triple helices and a high crystalline domain into the material. In vitro tests on rat Schwannoma cells showed that Schwann cell differentiation into myelinating cells was dependent on the specific collagen film being used, and was found to be stimulated in case of homogenization-treated samples. Finally DHT/EDC crosslinking treatment was shown to affect mechanical stiffness of films depending on collagen source and processing conditions.

Curcumin is a natural hydrophobic polyphenol found in the powdered rhizomes of Curcuma longa. Due to its capacity to interfere with many signalling pathways, it has been shown that curcumin has potential beneficial pharmacological effects including antioxidant, anti-inflammatory, anticarcinogenic properties. However, the use of curcumin is fairly restricted because of its poor water solubility, low bioavailability, inadequate tissue absorption and degradation at alkaline pH. In the present contribution, we first verified the anti-proliferative effects of natural curcuminoids towards two different cell lines derived from an ovarian and a breast adenocarcinoma cancer. Later, curcuminoids were successfully encapsulated into reconstituted oil bodies. Once encapsulated into the triacylglycerol cores of the reconstituted oil bodies, curcumin, the most hydrophobic and active of the three curcuminoids, was better stabilized in comparison with albumin stabilization. Oil body encapsulated curcuminoids showed the same effects on cancer cell viability as the free drug, confirming the great potential of natural oil bodies as micro/nano-capsules in drug delivery applications.

ZnO@Ag patchy nanostructures were demonstrated to be efficient and stable photocatalysts for the photodegradation of organic contaminants in aqueous solutions. The photoinduced charge transfer from the conduction band of ZnO toward the Fermi level of the noble metal was favored and exploited to enhance the photocatalytic efficiency of ZnO, with a mechanism based on hole stabilization. Naked ZnO and ZnO@Ag patchy nanostructures were demonstrated to degrade methylene blue, a model compound, in aqueous solution under 370− 800 nm light irradiation (100 mW cm−2); in particular, the introduction of silver nanoparticles allowed one to increment twice the constant rate of the reaction when fitted as pseudo-first-order kinetics. Furthermore, the degradation of 2,4dichlorophenol under direct sunlight irradiation was studied. The photo-oxidation catalyzed by patchy nanostructures was noticeably increased. In fact, the observed half time (t1/2) was reduced by almost 4 times in comparison with the value observed for bare ZnO.

Two of the most known properties of ZnO were used to improve the performance of a dye-sensitized solar cell (DSSC) using a nanoadduct formed by zinc oxide and the well-known ruthenium dye N719.The wurtzite form of zinc oxide suffers from piezoelectricity and its energetic levels are very similar to those of the most used inorganic semiconductor employed in DSSCs, that is, TiO2 . We demonstrate that the synthesis of a ZnO@N719 nanoadduct does not affect the electronic communication between the inorganic semiconductor and the organic dye. The I–V characteristics in the dark and under illumination highlight a photoactivity of the ZnO@N719 active layer with values of Jsc, Voc and fill factor comparable to the data reported in the literature. When a mechanical strain is applied to the ZnO@N719 film, a piezopotential is recorded and it depends on the intensity of the applied pressure. According to the piezotronic effect, mechanical strain contributes to increase the open circuit voltage by about 14%.

Silica nanoparticles (SiNPs) are widely studied nanomaterials for their potential employment in advanced biomedical applications, such as selective molecular imaging and targeted drug delivery. SiNPs are generally low cost and highly biocompatible, can be easily functionalized with a wide variety of functional ligands, and have been demonstrated to be effective in enhancing ultrasound contrast at clinical diagnostic frequencies. Therefore, SiNPs might be used as contrast agents in echographic imaging. In this work, we have developed a SiNPs-based system for the in vitro molecular imaging of hepatocellular carcinoma cells that express high levels of glypican-3 protein (GPC-3) on their surface. In this regard, a novel GPC-3 targeting peptide was designed and conjugated to fluorescent silica nanoparticles. The physicochemical properties, acoustic behavior, and biocompatibility profile of the functionalized SiNPs were characterized; then binding and uptake of both naked and functionalized SiNPs were analyzed by laser scanning confocal microscopy and transmission electron microscopy in GPC-3 positive HepG2 cells, a human hepatocarcinoma cell line. The results obtained showed that GPC-3-functionalized fluorescent SiNPs significantly enhanced the ultrasound contrast and were effectively bound and taken up by HepG2 cells without affecting their viability.

A new and simple method is presented to fluorinate the surfaces of poorly reactive hydrophobic polymers in a more environmentally friendly way using the protein hydrophobin (HFBII) as a nanosized primer layer. In particular, HFBII, via electrostatic interactions, enables the otherwise inefficient binding of a phosphate-terminated perfluoropolyether onto polystyrene, polypropylene, and low-density polyethylene surfaces. The binding between HFBII and the perfluoropolyether depends significantly on the environmental pH, reaching the maximum stability at pH 4. Upon treatment, the polymeric surfaces mostly retain their hydrophobic character but also acquire remarkable oil repellency, which is not observed in the absence of the protein primer. The functionalization proceeds rapidly and spontaneously at room temperature in aqueous solutions without requiring energy-intensive procedures, such as plasma or irradiation treatments.

The specific design of a collagen scaffold containing iron oxide nanostructures capped by a TiO2 (anatase) layer is reported. The TiO2 shell is proposed with a dual role: as an innovative and biocompatible cross-linker agent, providing binding sites to the protein moiety, through the well-known TiO2 chemical affinity towards carboxyl groups, and as a protective surface layer from oxidation for the paramagnetic core. Simultaneously, the presence of the nanostructures confers to the collagen gel the sensitivity to an external stimulus, i.e. the application of a magnetic field. The hybrid biomaterial was demonstrated to be healthy and was proposed as a smart scaffold for the on demand release of bioactive compounds. The tunable release upon magnetic field application of a model protein, i.e. myoglobin, was investigated. Myoglobin was loaded in the microporous material and the discharging was induced by consecutive magnet applications, obtaining the release of the protein with a high spatio-temporal and dosage control.

Oil bodies (OBs) are specialised organelles ubiquitously detected in plant oil seeds, which serve as lipid storage compartments. OBs consist of a hydrophobic core of triacylglycerol (TAGs), surrounded by a monolayer of phospholipids (PLs) embedded with some specific proteins with a size ranging from 0.5 to 2 μm. In this work, we report an easy method to reconstitute OBs starting fromtheir constituents and to encapsulate lipophilic molecules, i.e. the fluorescent fluorescein isothiocyanate (FITC) and carboxyfluorescein (CF), into reconstituted OBs. This methods allowed us to produce OBs 4- to 10-fold smaller (50–200 nm) than the native one and to obtain a good recovery (about 40%) of both the fluorescent compounds used in the present work. The properties of reconstituted OBs were investigated by a combination of Brewster angle microscopy, scanning force microscopy, ζ-potential techniques. OBs were stable and formed ordered monolayers when patterned on hydrophobic substrates whereas they showed a higher tendency to aggregate into larger, coalescing OBs when were deposited onto hydrophilic substrates or at the air/water interface. Furthermore, we verified the uptake of FITC- loaded OBs by the MCF-7 breast cancer cell line. Our results indicated that OBs could be envisaged as novel carriers to deliver hydrophobic bioactive compounds

A supramolecular adduct formed by the interaction among octadecylamine (ODA) and zinc oxide nanostructures was promoted. A stable dispersion of the ZnO@ODA adduct was obtained and characterized by means of thermogravimetric analysis and infrared and Raman spectroscopy. Then, the supramolecular adduct was spread at the air/water interface of a Langmuir trough. The presence of octadecylamine gave amphiphilic features to the ZnO@ODA adduct that was transferred from the air/water interface to solid substrates by Langmuir-Schaefer (LS) method. The transferred film was characterized by tunnel electron microscopy that highlighted rectangular well-shaped structures assembled by nanostructure of ZnO arranged in an ODA matrix. Piezoelectric feature of large LS film (1 cm2) was tested and a very promising response was observed as a consequence of the application of a pressure of 1 kPa.

Oil bodies (OBs) are micelle-like structures with an outer phospholipid monolayer embedding some specific proteins (oleosins) and surrounding a hydrophobic core of triacylglycerols (TAGs). Oleosins are alkaline hairpin-like proteins that are anchored into the OBs structure with their hydrophilic domains covering the surface. We performed surface pressure (Π) and Brewster Angle Microscopy investigations of reconstituted OBs (ROBs) and of trypsin digested ROBs. The obtained Π vs time isotherms clearly show the formation of a surface layer. Upon ROBs suspension injection into the subphase, a clear-cut Π enhancement is recorded, followed by a long plateau region for ROBs suspensions more concentrated than 12.5 μg/ml. The BAM analysis highlighted the presence of a dark background, ascribable to a 2D layer due to free components rearrangement and brilliant circular 3D domains, due to unaltered ROBs or small aggregates of ROBs. Increasing ROBs concentration, large domains appeared. We hypothesize that the presence of an excess of free TAGs in the 2D layer is crucial for the generation of such domains. We verified the generation of such typical structures, studying the behavior of a ROBs suspension (concentration of 12.5 μg/ml) with two different approaches: after injection under a concentrated TAGs floating layers and after digestion with trypsin. These two procedures resulted in similar effects since proteinase digestion is like to induce the same morphology of a TAGs excess.

The mechanisms of interaction between a tetrapyridyl-substituted porphyrin and Hg(II) and Cu(II) ions have been investigated by means of different spectroscopic techniques. Reflection spectroscopy investigations of the porphyrin Langmuir floating film and by polarization modulation infrared (IR) reflection adsorption spectroscopy at the air−water interface provided evidence of the active role played by the pyridyl substituents of the porphyrin in the interaction with the analyte. Such behavior seems to be very selective toward Cu2+ and Hg2+ ions, as demonstrated by the IR measurements in difference mode. UV−vis and IR characterizations suggest a deeply different interaction between the active molecules and the two analytes. In fact, the interaction of Hg2+ ions with the tetrapyrrolic derivative molecules involves both the pyridyl substituents and the central bite of the ring. On the other hand, in the case of Cu2+ ions, spectroscopic evidence suggests that the cupric ions interact with only the porphyrin peripheral substituents. A relevant fluorescence quenching of the Langmuir−Schaefer (LS) film is observed when even a 0.5 nM HgCl2 or 0.5 nM CuCl2 aqueous solution is fluxed on the LS film.

Carbon nanotubes are recent materials with an extremely appealing multiplicity of peculiar characteristics of paramount interest in contemporary advanced (nano)technologies. At the same time, the Langmuir–Blodgett technique allows to fabricate films with a substantial control and chance of modulation over thickness and molecular organisation. As a spontaneous outcome, this review deals with an actual subject of attention in up-to-date scientific investigations, i.e. the preparation, characterisation and applications of Langmuir–Blodgett films of pristine or functionalised single- or multi-walled carbon nanotubes in modern research.

Spiramycin is a macrolide antibiotic and antiparasitic that is used to treat toxoplasmosis and various other infections of soft tissues. In the current study, we evaluated the effects of α-cyclodextrin, β-cyclodextrin, or methyl-β-cyclodextrin supplementation to a synthetic culture medium on biomass and spiramycin production by Streptomyces ambofaciens ATCC 23877. We found a high stimulatory effect on spiramycin production when the culture medium was supplemented with 0.5% (w/v) methyl-βcyclodextrin, whereas α-cyclodextrin or β-cyclodextrin weakly enhanced antibiotic yields. As the stimulation of antibiotic production could be because of spiramycin complexation with cyclodextrins with effects on antibiotic stability and/or efflux, we analyzed the possible formation of complexes by physical−chemical methods. The results of Job plot experiment highlighted the formation of a nonhost@guest complex methyl-β-cyclodextrin@ spiramycin I in the stoichiometric ratio of 3:1 while they excluded the formation of complex between spiramycin I and α- orβ-cyclodextrin. Fourier-transform infrared spectroscopy measurements were then carried out to characterize the methyl-β-cyclodextrin@spiramycin I complex and individuate the chemical groups involved in the binding mechanism. These findings may help to improve the spiramycin fermentation process, providing at the same time a new device for better delivery of the antibiotic at the site of infection by methyl-β-cyclodextrin complexation, as it has been well-documented for other bioactive molecules.

New perylene monoimides, diimides and bis-diimides have been designed and synthetized. A detailed investigation of the synthesis of these compounds has also been performed in order to highlight the crucial factors for obtaining a specific class of molecules. Specifically, the attention has been focused on the synthesis of the intermediate perylene monoimides which are very useful precursors for many molecules difficult to obtain. Furthemore, two synthetic pathways have been developed for obtaining the bis-diimides variously substituted. These final compounds are predicted to mimic the excellent electron acceptor properties of fullerene derivatives and they can be used as building blocks to form 3D semiconducting materials.

Tetrapyrrolic macrocycles are largely used in the sensing of vari-ous analytes both in liquid and in gaseous phase, but thestrong electronic delocalization of this class of molecules makesdifficult to realize a selective active layer. To overcome thisproblem, in the present work it is proposed the synthesis of asupramolecular adduct of zinc oxide nanostructure and a free-base tetra- pyridyl substituted porphyrin. The electronic struc-ture of the two organic/inorganic compounds allows to ob-serve a surface-enhanced Raman scattering (SERS) of the por-phyrin vibrational bands. This phenom enon is quenched by thepresence of mercuric and cupric ions according to two differentmechanisms monitored and explained by means of time re-solved fluorescence spectroscopy. It was demonstrated thatother substances in complex matrices, such as the food ex-tracts, do not affect the electronic communication betweenZnO and porphyrin preserving the SERS effect and minimizingthe effect of interfering compounds.