Characterisation of nanomaterial hydrophobicity using engineered surfaces

Characterisation of engineered nanomaterials (NMs) is of outmost importance for the assessment of the potential risks arising from their extensive use. NMs display indeed a large variety of physico-chemical properties that drastically affect their interaction with biological systems. Among them, hydrophobicity is an important property that is nevertheless only slightly covered by the current physico-chemical characterisation techniques. In this work, we developed a method for the direct characterisation of NM hydrophobicity. The determination of the nanomaterial hydrophobic character is carried out by the direct measurement of the affinity of the NMs for different collectors. Each collector is an engineered surface designed in order to present specific surface charge and hydrophobicity degrees. Being thus characterised by a combination of surface energy components, the collectors enable the NM immobilisation with surface coverage in relation to their hydrophobicity. The experimental results are explained by using the extended DLVO theory, which takes into account the hydrophobic forces acting between NMs and collectors.

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Graphical abstract Determination of hydrophobicity character of nanomaterials by measuring their affinity to engineered surfaces.

     

Metabolomic Profiling of Fresh Goji (Lycium barbarum L.) Berries from Two Cultivars Grown in Central Italy: A Multi-Methodological Approach

The metabolite profile of fresh Goji berries from two cultivars, namely Big Lifeberry (BL) and Sweet Lifeberry (SL), grown in the Lazio region (Central Italy) and harvested at two different periods, August and October, corresponding at the beginning and the end of the maturation, was characterized by means of nuclear magnetic resonance (NMR) and electrospray ionization Fourier transform ion cyclotron resonance (ESI FT-ICR MS) methodologies. Several classes of compounds such as sugars, amino acids, organic acids, fatty acids, polyphenols, and terpenes were identified and quantified in hydroalcoholic and organic Bligh-Dyer extracts. Sweet Lifeberry extracts were characterized by a higher content of sucrose with respect to the Big Lifeberry ones and high levels of amino acids (glycine, betaine, proline) were observed in SL berries harvested in October. Spectrophotometric analysis of chlorophylls and total carotenoids was also carried out, showing a decrease of carotenoids during the time. These results can be useful not only to valorize local products but also to suggest the best harvesting period to obtain a product with a chemical composition suitable for specific industrial use. Finally, preliminary studies regarding both the chemical characterization of Goji leaves generally considered a waste product, and the biological activity of Big Lifeberry berries extracts was also investigated. Goji leaves showed a chemical profile rich in healthy compounds (polyphenols, flavonoids, etc.) confirming their promising use in the supplements/nutraceutical/cosmetic field. MG63 cells treated with Big Lifeberry berries extracts showed a decrease of iNOS, COX-2, IL-6, and IL-8 expression indicating their significant biological activity.     

Easy separation of Δ and Λ isomers of highly luminescent [Ir(III)]-cyclometalated complexes based on chiral phenol-oxazoline ancillary ligands

A new class of neutral cyclometalated iridium(III) complexes with enantiomerically pure C(1)-symmetric phenol-oxazolines (3a,b) have been synthetized in high yields and fully characterized. Resolution of the corresponding Δ(R) and Λ(R) or Δ(S) and Λ(S) isomers was easily achieved by conventional flash chromatography. The corresponding Δ and Λ helicities have been confirmed by CD spectroscopy and X-ray crystallography. Regarding the absorption and luminescence properties with unpolarized light, no significant difference between Δ and Λ isomers has been observed. A strong blue luminescence is observed for deaerated solutions of complexes 5a and 5b in CH(3)CN.     

Computational <Superscript>19</Superscript>F NMR. 1. General features

Fluorine-19 NMR chemical shifts have been calculated for a wide variety of fluorine-containing inorganic and organic molecules by relativistic DFT methods. The agreement with experimental values, spanning the whole range from ClF to FOOF, is satisfactory but somewhat less accurate than for comparable light nuclei. ¹⁹F shifts in uranium chlorofluorides have been analyzed in detail, and the poor agreement with experiment is partly rationalized.     

NMR properties of sedimented solutes

This perspective paper is intended to give some insights into the recently proposed technique of NMR of solutes sedimented by ultracentrifugation in a rotor used for solid state NMR experiments. Sedimented "states" correspond to molecules with very little reorientational capability in extremely concentrated solutions. They provide solid state NMR spectra comparable in quality with those of the best microcrystalline samples. Here we report some experiments to look for chemicals which affect the properties of the sediment, and we show that it is possible to fill the rotor in a true ultracentrifuge and then record the spectra. The latter possibility opens new horizons for NMR of sedimented systems.     

Monolayers of polyethilenimine on flat glass: a versatile platform for cations coordination and nanoparticles grafting in the preparation of antibacterial surfaces

A polyethylenimine (PEI) self-assembled monolayer (SAM) is prepared, capable of complexing silver and copper cations and of anchoring silver nanoparticles, exerting antibacterial activity against Escherichia coli and Staphylococcus aureus. Functionalized glassy surfaces have been fully characterized through spectroscopic techniques (UV-Vis spectroscopy, spectroscopic ellipsometry), atomic force microscopy imaging and quantitative Ag and Cu analysis (ICP optical emission spectroscopy).     

Solid-state NMR crystallography through paramagnetic restraints

Pseudocontact shifts (PCSs) measured by solid-state NMR spectroscopy (SS-NMR) on microcrystalline powders of a paramagnetic metalloprotein permit NMR crystallography. Along with other restraints for SS-NMR experiments, the protein molecular structure as well as the correct crystal packing are obtained.     

The quantum field as a quantum computer

It is supposed that at very small scales a quantum field is an infinite homogeneous quantum computer. On a quantum computer the information cannot propagate faster than c=a/τ, a and τ being the minimum space and time distances between gates, respectively. For one space dimension it is shown that the information flow satisfies a Dirac equation, with speed v=ζc and ζ=ζ(m) mass-dependent. For c the speed of light ζ−1 is a vacuum refraction index that increases monotonically from ζ−1(0)=1 to ζ−1(M)=∞, M being the Planck mass for 2a the Planck length. The Fermi anticommuting field can be entirely qubitized, i.e. it can be written in terms of local Pauli matrices and with the field interaction remaining local on qubits. Extensions to larger space dimensions are discussed.     

A Functional Equation Whose Unknown is \mathcal{P}([0,1]) Valued

We study a functional equation whose unknown maps a Euclidean space into the space of probability distributions on [0,1]. We prove existence and uniqueness of its solution under suitable regularity and boundary conditions, we show that it depends continuously on the boundary datum, and we characterize solutions that are diffuse on [0,1]. A canonical solution is obtained by means of a Randomly Reinforced Urn with different reinforcement distributions having equal means. The general solution to the functional equation defines a new parametric collection of distributions on [0,1] generalizing the Beta family.     

Physicochemical characterization of acrylamide/bisacrylamide hydrogels and their application for the conservation of easel paintings

Acrylamide chemical gels have been synthesized to obtain systems with mechanic and hydrophilic properties suitable for the cleaning of works of art. The gel characteristics were tailored by changing the polymer percentage present in the final hydrogel formulation from 2 to 10% w/w. Two different hydrogels have been selected in this interval for an in depth characterization (i.e., S 4% w/w and H 6% w/w). Water retention properties of the gels along with the free water index have been determined by the combination of standard dehydration tests and differential scanning calorimetry (DSC) measurements. The gels' structure has been determined by scanning electron microscopy (SEM) and small angle X-ray scattering (SAXS). The water retention capacity of hydrogel, H, was also determined. Cleaning tests on easel painting replicas, performed with both hydrogels loaded with an aqueous detergent system, showed good results in the removal of a widely used synthetic adhesive and hence offered these gels as a real alternative to the widely applied physical gel methodology with the advantage of being a residue-free technique. A preliminary SAXS investigation confirms the persistence of the detergent system nanostructure inside the hydrogel.