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In the manifold of materials for Volatile Organic Compound (VOC) sensing, graphene related materials (GRMs) gain special attention thanks to their versatility and overall chemico-physical tunability as a function of specific applications. In this work, the sensing performances of graphene-like (GL) layers, a new material belonging to the GRM family, are tested against ethanol and n-butanol. Two typologies of GL samples were produced by employing two different approaches and tested in view of their application as VOC sensors. The experiments were performed under atmospheric pressure, in dry air, and at room temperature and demonstrated that the sensing capabilities are related to the film surface features. The results indicated that GL films are promising candidates for the detection of low concentrations of VOCs at room temperature. The present investigation thus paves the way for VOC sensing optimization using cost-effective and easily scalable materials. © 2018 Author(s).

Graphene-like (GL) layers were prepared through a two steps oxidation/reduction method starting from a high surface carbon black, and pH of the GL layers in water suspension was varied. The effect of pH of such suspension on the morphology of self-assembled GL films has been studied. Zeta potentials of the water suspensions were measured to estimate the stability of the suspension at several pH values and to select the samples for deeper investigation by atomic force microscopy (AFM). AFM measurements on four different samples are then described and discussed. The reported results show how the surface roughness and morphology are affected by the pH in the preparation process: in particular, the lowest pH sample exhibits a granular surface, while at higher pH more regular morphologies are produced, with interesting observations as concerns the thickness of some surface features. The observations are interpreted in terms of the forces acting in water suspension and of the role of hydrophobic or hydrophilic behaviors. The results demonstrate the possibility to tune the surface properties of GL films by simply acting on the pH of the suspension during the fabrication, and help to understand the microscopic physical mechanisms involved in the film assembly. (C) 2015 Elsevier B.V. All rights reserved.

Hydrophilic carbonaceous nanoparticles (HNPs) of uniform sizes with a good degree of dispersion in water were produced from a commercial carbon black by nitric acid treatment. The surface treatment, performed at different reaction times, generates a variable number of oxygen functional groups, mainly carboxylic, which enhance the nanoparticles hydrophilicity and heavy metal adsorption capability. The HNPs were characterized by a number of analytical techniques, including FTIR spectroscopy, thermal and elemental analysis, N2 adsorption, dynamic light scattering, and zeta-potential measurements. The acid–base properties of the functional groups on the HNPs surface were also investigated by coulometric–potentiometric titrations. Cadmium adsorption tests were carried out in stirred reactors containing colloidal aqueous suspensions of HNPs and HNPs supported over silica. The effects of several parameters, such as the cadmium concentration, the temperature, and the solution pH, were studied. Sorbents showed an appreciable cadmium adsorption capability at different temperatures and in a wide range of pH values comparable or superior to several carbon-based sorbents, indicating a feasible use in commercial units.

The different thermal behaviors and solubilities of large and structurally different polycyclic aromatic hydrocarbon (PAH) mixtures featuring coal tar pitch (CP) and naphthalene synthetic pitch (NP) samples could be read in light of their different molecular weight (MW) distribution and spectroscopic features. The number-average MW obtained by mass spectrometry for CP (417 Da) and NP (691 Da) resulted to be lower in comparison to the values evaluated by size-exclusion chromatography (SEC) (796 and 824 Da for CP and NP, respectively) because of the different response of the detector of mass spectrometry to low- and high-MW components. Hence, SEC showed to be more suitable for the analysis of PAH mixtures overlapping and covering a higher mass range in comparison to mass spectrometry. Insights into structural PAH features were given by means of spectroscopic analysis [infrared (IR), ultraviolet-visible (UV-vis), and fluorescence], allowing for the discrimination between different families of PAHs as ortho-fused PAHs and rylenes interspersed with aliphatic (mainly naphthenic) groups, mainly featuring CP and NP, respectively. Besides showing the different aromaticity and aliphatic/aromatic hydrogen distribution, the improvement of Fourier transform infrared (FTIR) and UV-vis absorption analysis put also in evidence the contribution of carbon-rich particle impurities and PAH aggregates in CP and NP, respectively.

Organic (bio)electronics appears to be the first target for competitive exploitation in the materials science of eumelanins, black insoluble photoprotective human biopolymers. Nonetheless, the low conductivity of these pigments is limiting the implementation of eumelanin-based devices. Here we present a novel organic/organic hybrid material (EUGL) by integration of conductive graphene-like (GL) layers within the EUmelanin pigment (EU). GL layers were obtained by a two-step oxidation/reduction of carbon black. The stability of GL layers over a wide pH range and the self-assembling tendency place this material in a leading position for the fabrication of hybrid materials in aqueous media. EUGL was obtained by inducing the polymerization of eumelanin precursors (5,6-dihydroxyindole, DHI and 5,6-dihydroxyindole-2 carboxylic acid, DHICA) in aqueous media containing GL layers. The new material featured promising biocompatibility and an increased conductivity with respect to eumelanin by four orders of magnitude.

Graphene-like (GL) layers and eumelanin-based graphene-like (EUGL) hybrids have been investigated through THz time domain spectroscopy. The interest in these materials lies on their peculiar chemical-physical properties: the former are conductive water stable materials, whereas the latter are biocompatible materials with good conductive and adhesive properties. Both exhibit promising optoelectronic and bioelectronic applications. We measured mixtures of GL layers or EUGL hybrids with KBr, shaped in pellets with uniform thickness, in order to circumvent problems related to sample inhomogeneity and roughness. A mean field theory was applied to extract direct information on permittivity and conductivity. Data have been carefully fitted through the Drude-Smith theory, confirming the conductive nature of the hybrid materials. The results show that EUGL hybrid-based devices can be promising for the next generation of printable bio-circuits.

The structures of the capsular polysaccharides (CPSs) of the two clinical isolates Acinetobacter baumannii SMAL and MG1 were elucidated. Hot phenol/water extractions of the dry biomasses, followed by enzymatic digestions and repeated ultracentrifugations led to the isolation of polysaccharides that were negative in Western blot analysis utilizing an anti-lipid A antibody, thus proving that they were not the LPS O-antigens but CPSs. Their structures were established on the basis of NMR spectroscopy and GC-MS analyses. The A. baumannii MG1 CPS consisted of a linear aminopolysaccharide with acyl substitution heterogeneity at the N-4 amino group of QuipN4N: 4)-alpha-D-GlcpNAc-(1 -> 4)-alpha-L-GalpNAcA-(1 -> 3)-beta-D-QuipNAc4NR-(1 -> R = -3-hydroxybutyrryl or acetyl. The repeating unit of the CPS produced by strain SMAL is a pentasaccharide, already reported for the O-antigen moiety from A. baumannii strain ATCC 17961: beta-D-GlcpNAc3NAcA-(1 down arrow 4) 6)-beta-D-Glcp-(1 -> 3)-beta-D-GalpNAc-(1 -> 3)-alpha-D-Galp-(1 -> 6)up arrow beta-D-GlcpNAc-(1

The structure of the carbohydrate backbone of the core-lipid A region of the lipooligosaccharide (LOS) of the alkaliphilic and slightly halophilic bacterium Halomonas sp. has been elucidated. The LOS was fully deacylated, dephosphorylated, and reduced at the free reducing end. The structure, obtained by means of compositional analysis, 2D NMR spectroscopy, and MALDI mass spectrometry, was determined as the following: Download : Download full-size image All sugars are d -pyranoses; Hep is l -glycero- d -manno-heptose and Kdo is 3-deoxy- d -manno-oct-2-ulosonic acid.

Chondroitin sulfate (CS), a constituent of proteoglycans, is a key component of the connective tissues and it is widely used as a precautionary drug for joint diseases; for this reason, the increased demand of this polysaccharide has posed the problem to identify new and secure sources of this product. In this context, CS from the cartilage of the lesser spotted dogfish (Scyliorhinus canicula, a cartilaginous fish) was isolated and investigated through chemical and spectroscopical techniques. The structural elucidation was performed on the entire polysaccharide and confirmed analyzing the products obtained via ABC lyase treatment. As a result, its compositional analysis disclosed the occurrence of CS-A, CS-C, CS-D, and CS-0S motifs in the ratio of 41, 32, 19.8, and 8.2%, respectively. Additionally, two different glycopeptides were isolated and characterized via NMR, providing information on the linkage oligosaccharide region joining the glycosaminoglycan chain to the core protein. Therefore, chondroitin sulfate from Scyliorhinus canicula appears very similar to that isolated from shark, a cartilaginous and taxonomically related fish, with the main difference residing in the major percentage of the CS-A motif. In the light of the results obtained, Scyliorhinus canicula chondroitin sulfate possesses a chemical structure compatible for the formulation of commercial and pharmaceutical products.

The structure of the capsular polysaccharide produced from the type strain of Agrobacterium rubi DSM 6772 is demonstrated by means of chemical and spectroscopical methodologies. It is constituted from the quite rare monosaccharide 6-deoxy-L-talose, involved in alternating alpha-(1 --> 2) and alpha-(1 --> 3) linkages. This simple backbone is further complicated from the occurrence of O-acetyl substituents located always at O-2 of the O-3 substituted 6-deoxy-talose. This decoration is not stoichiometric and it depends on the growth stadium of the bacterium, leading to an almost regular acetylation pattern only at the stationary phase, where all the potential positions are substituted.

We developed a new approach for producing graphene-like (GL) materials through a two-steps oxidation/reduction method starting from a nanostructured (high surface) carbon black, a versatile carbonaceous material prone to be structurally and chemically modified in quite mild wet conditions. Atomic Force Microscopy and zetapotential measurements allowed to model the assembling mechanisms and the role of hydrophobic interactions, demonstrating the possibility to easily tune the surface morphology. GL materials have been then employed in a large variety of hybrid materials for innovative applications, and characterized by chemical, electrical, structural and spectroscopic techniques. With Metal-Organic Frameworks, GL produced conducting composites with electrical conductivity tunable by changing the concentration of the parent materials; Eumelanin/GL and TiO2-nanoparticles/GL were also studied for photocatalysis and biosensors applications.