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.

An alkoxy-substituted poly(phenylene thiophene) is used in order to suspend single-walled carbon nanotubes in an organic solvent. The suspension is spread on the air–water interface of a Langmuir trough and the floating film is characterized by means of Brewster angle microscopy and UV-visible reflection spectroscopy and the compression isotherm is recorded. The polymer/carbon-nanotube blend is transferred onto different substrates using the Langmuir–Blodgett technique. AFM measurements indicate the formation of globular structures for the samples transferred at low surface-pressure values and a tubular morphology for high-pressure-deposited samples. AFM analysis is repeated on a sample exposed to soft X-rays for about 5 h and a highly organized structure of bundles of carbon nanotubes rises up. Samples with different numbers of layers are transferred onto ITO substrates by means of the Langmuir–Blodgett method and are tested as photocathodes in a photo-electrochemical cell. A Voc of 0.18 V, an Isc of 85.8mA, FF of 40.0%, and h of (6.23T103 )% are obtained.

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.

A conformational switching of bis(zinc octaethylporphyrin) was observed, for the first time, in a Langmuir-Schaefer film as a consequence of appropriate host-guest interactions. The spectral changes are completely reversible and the high sensitivity (similar to 20 ppb) and specificity for aromatic amines open up interesting prospects of this functional material as a performing sensor for amines.

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.

ABSTRACT The development and characterization of a novel bioactive polymer based on the immobilization of glucose oxidase enzyme (GOx) in a polyvinyl alcohol (PVA) film showing antibacterial activity is presented. The PVA-GOx composite material was extensively characterized by UV-vis, X-ray Photoelectron (XPS) spectroscopy and by Fourier Transform Infrared (FTIR) spectroscopy to verify the preservation of enzyme structural integrity and activity. The antimicrobial activity of this composite material against Escherichia coli and Vibrio alginolyticus was assessed. Furthermore the lysozyme-like activity of PVA-GOx was highlighted by a standard assay on Petri dishes employing Micrococcus lysodeikticus cell walls. The findings from this study have implications for future investigations related to the employment of PVA-GOx system as a composite material of pharmaceutical and technological interest.

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.

Ethane-bridged Zn porphyrins dimers (ZnPP) have been deposited by Langmuir–Schäfer (LS) deposi- tion technique onto proper transducer layers for surface plasmon resonance (SPR) and magneto-optical surface plasmon resonance (MO-SPR) characterization techniques performed in controlled atmosphere. This last tool has emerged as a novel and very performing sensing technique using as transducer layers a combination of noble and magnetic layers deposited onto glass substrates. A magnetic actuation allows recording a magneto optical SPR signal which ensures best gas sensing performances in terms of signal to noise ratio, sensitivity and limit of detection parameters. Primary and secondary amines in vapour phase have been used as sensing analytes and a possible explanation of the mechanism as well as of the dynamics of the interaction with the sensing Zn Porphyrin layers is provided

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%.

This work reports on the structural and spectroscopic properties, as well as the gas-sensing performance, of ethane-bridged Zn porphyrin dimers (ZnPP) in Langmuir−Schafer (LS) thin ̈ films toward volatile organic compounds in a magneto-optical surface plasmon resonance (MOSPR) configuration. Structural and spectroscopic properties of ethane-bridged ZnPP thin films deposited onto proper Au/Co/Au magneto-optical substrates were inspected in dry air conditions and after exposure to amine vapors by means of IR spectroscopy, scanning probe microscopy, and MOSPR techniques. The molecular organization of the thin films deposited by the LS technique is investigated. The overall results suggest the presence in all cases of mainly the anti-conformer of the investigated porphyrin dimers. The strong interaction between n-butylamine vapors at high concentration and Zn porphyrin thin layers leads to a great conformational change in the porphyrin structure, which is linked to a change in the optical anisotropy of the realized LS layer.

Thin film of ethane bridged Zn-Porphyrin dimers is deposited via Langmuir-Schäfer (LS) technique over Au/Co/Au transducers properly realized on glass substrates. They have been tested as sensing layers in the novel Magneto-Optical Surface Plasmon Resonance (MO-SPR) sensor for monitoring the controlled adsorption of molecules of a volatile compound such as tert-butylamine vapours. The sensing performance of the organic layer onto the novel MO-SPR transductor sensor has been evaluated.

Glass micromachining is a basic technology to achieve microfluidic networks for lab-on-a-chip applications. Among several methods to microstructure glass, the simplest and most widely applied is wet chemical etching (WE). However, accurate control of the reaction conditions to perform reproducible, fast and safe glass etching is not straightforward. Herein, microwave-assisted WE is demonstrated to intensify the glass etching action under safe working and finely monitored operative conditions and to produce smooth deep channels in short processing times with reduced underetching effects.

From the inscription of the General Post Office in Washington DC: “The stamp is the propagator of news, links between distant families, messenger between friends, solace in solitude, a vehicle for commerce and industry, an element of human progress, promoting brotherhood, peace, goodwill among men and nations”. It’s hard to imagine how much history can be held in a small piece of paper and how many purposes this little object was destined to have. This is why postage stamps have reached so much importance and interest, which they began to be considered as work of art actually. In order to see beyond the careful eye of the philatelist, FTIR (Fourier Transform Infrared Spectroscopy) in ATR (Attenuated Total Reflection) mode has been successfully employed in material characterization of many stamps. Samples since 1861, year of the unification of the Kingdom of Italy, until to date, across a vast philatelic collection, has been characterized in this study. The immediate response of this type of spectroscopic technique let to achieve significant data information, which led to design history changes in paper making technologies. The first mail stamps published in Italy portrayed King Vittorio Emanuele II and it showed to be made of sheet of cellulose paper. Going forward in years, many differences were detected in paper composition. The mail stamps were also observed by fluorescence microscopy, in order to determine differences in the application of fluorescence. The analyses were performed without any alteration of the samples and no removal of material was needed, which represents the “conditio sine qua non” for investigations on these kinds of Cultural Heritage.

Abstract Deep eutectic solvents (DESs) are emerging as a new class of green solvents with the potential to replace organic solvents in several fundamental and applied processes. In this work, we offer an unprecedented characterization of the behavior of the bacterial photosynthetic reaction center (RC) from Rhodobacter sphaeroides in a series of choline chloride based DESs. RC is a membrane-spanning three-subunit pigment protein complex that, upon illumination, is capable of producing a stable charge-separated state. Thus, it represents the ideal model for carrying out basic studies of protein solvent interactions. Herein, we first report that, in many DES mixtures investigated, RC (a) is stable, (b) is capable of generating the charge-separated state, and (c) is even able to perform its natural photocycle. It proved, indeed, to be effective in reducing quinone molecules to quinol by withdrawing electrons from cytochrome c. As an example of biotechnological application, a photoelectrochemical cell based on DES-dissolved RC has also been designed and successfully employed to generate photocurrents arising from the reduction of the electron-donor ferrocenemethanol.

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.

Single-walled carbon nanotubes (SWCNTs) were suspended in 1,2-dichloroethane by noncovalent functionalization with a low-band-gap conjugated polymer 1 alternating dialkoxyphenylene−bisthiophene units with benzo-[c][2,1,3]thiadiazole monomeric units. The suspended 1/SWCNT blend was transferred onto different solid substrates by the Langmuir−Schaefer deposition method, resulting in films with a high percentage of aligned nanotubes. Photoelectrochemical characterization of 1/SWCNT thin films on indium−tin oxide showed the benefits of SWCNT alignment for photoconversion efficiency.

This work demonstrates that lipid-detergent mixed micelles can be employed successfully in order to achieve and modulate the transfer of bio-active hydrophobic compounds into lipid carriers by means of a simple and bio-safe procedure. In our specific investigation, liposome preparations incorporating mixtures of natural carotenoids with high lycopene content were developed and characterized, aiming to obtain formulations of potential nutraceutical and pharmaceutical interest. The starting material was a solvent-free high-quality lycopene rich oleoresin (LRO) obtained by extracting a freeze-dried tomato matrix with supercritical carbon dioxide (SC-CO2). Mixed micelles containing 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and cholate were loaded with LRO antioxidants by means of two slightly different procedures, which surprisingly resulted in significant differences in both quality and quantity of incorporated carotenoids. In particular, the selective incorporation of (all-E)-lycopene was achieved by extracting the oleoresin with a pre-formed cholate/POPC micelle suspension whilst (Z)-isomers were preferentially integrated when treating a POPC/LRO mixed film with cholate. The micelle to vesicle transition (MVT) method was employed in order to produce vesicles of well-defined lamellarity and size. Visible and infrared (IR) spectroscopy as well as Dynamic Light Scattering (DLS) and Transmission Electron Microscopy (TEM) measurements allowed the extensive characterization of LRO-loaded micelles and liposomes. The antioxidant potential of preparations was assessed by measuring the radical scavenging activity towards the coloured radical cation of 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonate) (ABTS). Important information about the reliability of different approaches for antioxidant capacity evaluation of micelle and liposome preparations was gained and the successful incorporation of LRO antioxidant power in a bio-deliverable water-dispersed form was demonstrated.

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.

1 MeV copper ions were implanted in polycarbonate (PC) matrices with fluences ranging from 5 × 1013 ions cm-2 to 1 × 1017 ions cm-2 in order to modify the optical and electrical properties of the polymer host. Increasing the ion fluence, an increase of the overall absorption and a redshift of the optical band gap were observed, from the initial value of 3.40 eV for the pristine PC to 0.80 eV measured for 1 × 1017 ions cm-2. For fluences above 5 × 1014 ions cm-2 a broad optical absorption bands at 450-475 nm and 520 nm were observed and, from 1 × 1016 ions cm-2, an additional band appeared at 570 nm. Both bands redshift when the fluence is increased. On the contrary, the optical response of the highest fluence sample is characterized by an overall band at 580 nm. The chemical modifications observed in the polymer ranges from induced -OH stretching, CO and -CC- double bonds and -CC and CH triple bonds formation, as the ion fluence increases. The implantation process affects the electrical properties of the polymer inducing a strong reduction in sheet resistance when ion fluence exceeds 5 × 1016 ions cm-2. A value of ∼7.1 × 107 Ω/sq has been obtained for the highest fluence, i.e. about 10 order of magnitude lower than the pristine PC.

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.

Time travel through 150 years of Italian postage stamp issues has allowed defining the evolution of the recurring pigments in stamp designs by means of Raman and FTIR spectroscopy. Numerous exemplars have been analyzed, covering the entire production of stamps for both the Italian Kingdom and Republic. Raman and FTIR spectra showed the changeover from Prussian blue to copper phthalocyanine inks in 1958. The entire succession for red inks was also recognized to develop from the original cinnabar to red ochre and minium and finally to red azo pigments. The changes in orange printing ink proceeded on a similar path. The first orange Italian exemplar was printed employing a mixture of chrome orange and red ochre. In 1929 this combination was replaced by azo pigments. Green stamps belonging to the first issues entailed the choice of blue and orange inks, namely chrome orange and Prussian blue. Later on, an ink composed mainly of phthalocyanine was employed as the green dye. The merging of data coming from Raman microscopy and FTIR-ATR spectroscopy, both non-destructive techniques, has allowed the characterization of stamp designs and potentially provides direct and fast evidence for the recognition of forged exemplars.

The evolution of the connections between Art and Science have been continually developing over the last few years. These links have led to many scientific characterisation and analysis techniques becoming increasingly applied to study works of art and artifacts. Today’s science and technology developments have led to many different approaches being used in the study of Cultural Heritage. New non-destructive methodologies allow one to apply physical and chemical analysis methods to valuable objects. Fourier transform infrared (FT-IR) spectroscopy has become a particularly useful technique in this field for the characterization of material composition; in particular, the use of the attenuated total reflection (ATR) sampling technique allows one to analyse a wide range and type of valuable objects without causing any damage to the samples. Capable of seeing beyond the careful eye of the restorer or of the art historian, the FT-IR/ ATR technique has been successfully employed in the material characterization of many different samples coming from the world of art. The first systematic studies using spectroscopic investigations on stamps were performed using both the FT-IR and Raman spectroscopic techniques. The immediate and detailed response from this type of study has led to a large and very significant amount of data and informainformation becoming available. Information which gives, not only an insight into the materials that compose a particular work of art, but also provide guidelines that supply further awareness important to conservative and restoration treatments. Discovering the ancient secrets of the artists and the real composition of art objects can be the key enlightening cases under study, which until that moment had been unresolved.

A Fourier transform infrared (FT-IR) spectroscopy study on the entire Italian postage stamps production is presented in this work. Crossing 150 years of issues from the unification of Italy until today, a time line of the major components constituting the stamps has been defined, based on the wide spectral database built on the basis of the numerous analyzed exemplars. Even though it is easy to find reports about stamps’ issues history, information arising from these investigations contributes to throw light upon the substances incorporated in the stamps, which could be described as hybrid or composite materials (a sort of undisclosed or hidden story). As a result of the whole spectra acquired in attenuated total reflectance (ATR) mode, changes in paper composition showed the transition from the protein sizing glue to starch sizing; also the employment of kaolin varied through time. First it was used as the extender in the pigment−medium mixture, and finally it constituted the coating on the stamp surface. Also the chemical composition of the adhesive gum on the rear side of stamps has been subjected to modifications, as well as the front side. The earliest back glue was a protein-based adhesive; then it was replaced by gum arabic first and by poly(vinyl acetate) (PVAC) later. FT-IR spectroscopy, supported by the detailed database developed, has been applied, for the first time, in the very useful detection of two counterfeit samples: a fake of the famous Gronchi Rosa, issued in 1961, and a regummed 2 cent red stamp, issued in 1865. The information held in the whole spectral data has been selected and employed in the principal component analysis (PCA) statistical analysis.

In the present manuscript it is reported a study carried out by means of micro-Raman and infrared spectroscopy on banknotes used in Italy during more than 50 years, since 1947 until 2001. For each specimen, three different features of the banknote (serial number, watermark and security mark) were considered and the measurements were repeated on three different banknotes of the same type. Differences were revealed in the paper banknote composition, red color used for the security mark and serial number black printing ink. Then, two certified fakes were analyzed and significant shifts on the main peak of red color pigment were revealed

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.

Porphyrins are tetrapyrrolic macrocycles with a fascinating and multifarious variegation of properties of essential significance in up-to-date and leading technologies. From a different point of view, the Langmuir–Blodgett technique allows the immobilisation of films with an accurate regulation of molecular organisation and thickness. As a logical upshot, this manuscript concerns a substantial object of consideration in contemporary research, the utilisation of Langmuir–Blodgett multilayers of porphyrins in sensing elements for the detection of analytes in different matrices. Investigations on themorphological, optical, structural and surface characteristics of these films are remarkably related to the significant properties of sensors with the ultimate goal of rationalising the innermost intercourses between the sensing behaviour and the peculiarities and molecular organisation brought about by the deposition method. The integration of the typical electrical and optical characteristics of porphyrins with the potentialities of the Langmuir–Blodgett multilayer has originated not only encouraging projects but has afforded also certainties on the accomplishment of operative chemical sensors.

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.

Amyloid supramolecular assemblies have found widespread exploitation as ordered nanomaterials in a range of applications from materials science to biotechnology. New strategies are, however, required for understanding and promoting mature fibril formation from simple monomer motifs through easy and scalable processes. Noncovalent interactions are key to forming and holding the amyloid structure together. On the other hand, the halogen bond has never been used purposefully to achieve control over amyloid self-assembly. Here we show that single atom replacement of hydrogen with iodine, a halogen-bond donor, in the human calcitonin-derived amyloidogenic fragment DFNKF results in a super-gelator peptide, which forms a strong and shape-persistent hydrogel at 30-fold lower concentration than the wild-type pentapeptide. This is remarkable for such a modest perturbation in structure. Iodination of aromatic amino acids may thus develop as a general strategy for the design of new hydrogels from unprotected peptides and without using organic solvents.

A novel bis-pyrene tweezer anchored on a rigid polyoxometalate scaffold fosters a unique interplay of hydrophobic and electrostatic supramolecular interactions, to shape carbon nanostructures (CNSs)-based extended architectures.

A Langmuir film of bis(zinc octaethylporphyrin) (ZnPP) was characterised at the air–water interface and its syn–anti conformation switching induced upon addition of aromatic amines was studied by infrared and UV–vis reflection spectroscopic methods. The highly specific interaction of ZnPP with aromatic amines was maintained even after the floating film was transferred onto solid supports by the Langmuir– Schaefer (LS) technique, enabling us to selectively sense aromatic amines at concentrations as low as 20 ppb. Furthermore, LS ZnPP active layer selectivity was evaluated in the presence of aliphatic amines.

During the Middle Ages in Europe, a different post-mortem funerary custom came to be used in order to transport and solemnly dispose of the bodies of high-status individuals. Because of their high degree of mobility, most medieval kings and queens rarely died where they had planned to be buried; thus, they had to be moved to the place of burial. Ancient writings describe some post-mortem funerary practices carried out to facilitate transport, such as boiling or burning of bodies after death. The remains of Henry VII of Luxembourg were analysed in order to determine which post-mortem practices were utilized. A detailed chemical-physical analysis was conducted to highlight the changes in the bone matrix due to post-mortem alteration. Boiling and burning leave different marks in the bone that could be differentiated through the analysis of the inorganic and organic components of the bone. Accordingly, anthropological, X-ray diffraction (XRD), infrared spectroscopy (FT-IR), collagen ratio, and scanning electron microscopy (FE-SEM/EDAX) analysis were performed on two different bone fragments: cranial and tibial shaft. This multidisciplinary approach has enriched scientific understanding of the post-mortem practices to which the skull and tibial shaft of Henry VII were subjected. The results highlight that the tibial shaft was treated under higher temperature respect to the skull. Furthermore, this analysis also shed light on the state of preservation of the bone fragments analysed and has allowed us to initiate more complex molecular analysis, as well as ancient DNA analysis.

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.

This invention pertains to gaseous analytes sensor devices comprising organic thin film transistor and, in particular, sensors able to perform the enantiomeric discrimination of gaseous analytes. The organic thin films are characterized by comprising a compound of formula (I)

La presente invenzione riguarda dispositivi sensori analiti gassosi comprendenti transistor a film sottile organico e, in particolare, sensori in grado di effettuare la discriminazione enantiomerica di analiti gassosi. I film sottili organici sono caratterizzati dal fatto di comprendere un composto di formula (I).

This invention pertains to gaseous analytes sensor devices comprising organic thin film transistor and, in particular sensors able to perform the enantiomeric discrimination of gaseous analytes. The organic thin films are characterized by comprising a compound of formula (I).