Characterization of gas phase aggregates of bis(2-ethylhexyl)sulfosuccinate (AOT) and divalent metal ions. Elimination of radical species in the decomposition pathways of even-electron [AOTMIICl2]– anions

Structure and properties of even-electron anionic species formed by bis(2-ethylhexyl)sulfosuccinate (AOT) and divalentmetal ions (MII) with stoichiometry [AOTMIICl2]– have been investigated by using electrospray ionization and different mass spectrometry techniques, such as high resolution, accurate mass measurements, collision-induced dissociation (CID) multiple-stage mass spectrometry.Owing to CID, eliminations of neutrals,mainly consisting in hydrochloric acid, 2-ethyl-1-hexene and 2-ethylhexanol, and an unexpected loss of an alkyl radical have been observed. The radical anions [C4HO6SMIICl]–• so produced have been characterized by MS3 experiments. Density functional theory calculations have been carried out for investigating structure and stability of the ionic species formed in the decomposition pathways

Self-assembly in surfactant-based mixtures driven by acid–base reactions: bis(2-ethylhexyl) phosphoric acid– n-octylamine systems

Structural and dynamic features of bis(2-ethylhexyl) phosphoric acid (HDEHP)–n-octylamine (NOA) mixtures as a function of the NOA mole fraction (XNOA) have been investigated by SAXS, WAXS, IR, dielectric spectroscopy and polarized optical microscopy. In the 0 ¡ XNOA , 0.5 range, mixtures are transparent liquids, while the abrupt formation of a waxy solid characterized by an hexagonal bidimensional structure occurs at XNOA = 0.5. Such a composition-induced phase transition results from the synergetic effect of the progressive increase in number density of ordered HDEHP–NOA nanodomains with XNOA. Mainly driven by an HDEHP to NOA proton transfer, the increase of structural order with XNOA arises from the progressive substitution of loosely hydrogen bonded HDEHP–HDEHP aggregates with strongly bonded NOA–HDEHP ones. Analysis of SAXS patterns at temperatures in the 10–70 uC range emphasized that these local structures are scarcely impacted by an increase of thermal fluctuations. Effects due to the steric compatibility between HDEHP and NOA apolar moieties have been highlighted. Overall, the results allow us to emphasize the role of specific polar and apolar interactions joined to steric effects in regulating the molecular organization in surfactant mixtures and can be used to design novel materials with planned physico-chemical properties

Dibutyl phosphate/propylamine mixtures show supra-molecular slow building up under magnetic field

Liquids with anisotropic local nanostructures which are able to be oriented by a magnetic field can give birefringence. Usually magnetically-induced birefringence is low owing to the low magnetic energy of molecules and to the averaging effect due to thermal agitation. At the same time, the response is usually very fast given the typical timescales of molecular orientational dynamics (nanoseconds). However, we show that the dibutyl phosphate/propylamine liquid mixture is characterized by an extremely slow response (hours) to the magnetic field and by an intense overall effect (Δn/λ ≈ −0.1m-1at 1 Tesla).This surprising behavior has been interpreted as a manifestation of a novel phenomenon of progressive building up of larger and larger internally ordered hetero-associates driven by the magnetic field and involving strongly interacting amphiphiles

Degrees of freedom effect on fragmentation in tandem mass spectrometry of singly charged supramolecular aggregates of sodium sulfonates

The characteristic collision energy (CCE) to obtain 50% fragmentation of positively and negatively single charged non-covalent clusters has been measured. CCE was found to increase linearly with the degrees of freedom (DoF) of the precursor ion, analogously to that observed for synthetic polymers. This suggests that fragmentation behavior (e.g. energy randomization) in covalent molecules and clusters are similar. Analysis of the slope of CCE with molecular size (DoF) indicates that activation energy of fragmentation of these clusters (loss of a monomer unit) is similar to that of the lowest energy fragmentation of protonated leucine-enkephalin. Positively and negatively charged aggregates behave similarly, but the slope of the CCE vs DoF plot is steeper for positive ions, suggesting that these are more stable than their negative counterparts

3D MODELS FOR ALL: LOW-COST ACQUISITION THROUGH MOBILE DEVICES IN COMPARISON WITH IMAGE BASED TECHNIQUES. POTENTIALITIES AND WEAKNESSES IN CULTURAL HERITAGE DOMAIN

Nowadays, 3D digital imaging proposes effective solutions for preserving the expression of human creativity across the centuries, as well as is a great tool to guarantee global dissemination of knowledge and wide access to these invaluable resources of the past. Nevertheless, in several cases, a massive digitalisation of cultural heritage items (from the archaeological site up to the monument and museum collections) could be unworkable due to the still high costs in terms of equipment and human resources: 3D acquisition technologies and the need of skilled team within cultural institutions. Therefore, it is necessary to explore new possibilities offered by growing technologies: the lower costs of these technologies as well as their attractive visual quality constitute a challenge for researchers. Besides these possibilities, it is also important to consider how information is spread through graphic representation of knowledge. The focus of this study is to explore the potentialities and weaknesses of a newly released low cost device in the cultural heritage domain, trying to understand its effective usability in museum collections. The aim of the research is to test their usability, critically analysing the final outcomes of this entry level technology in relation to the other better assessed low cost technologies for 3D scanning, such as Structure from Motion (SfM) techniques (also produced by the same device) combined with dataset generated by a professional digital camera. The final outcomes were compared in terms of quality definition, time processing and file size. The specimens of the collections of the Civic Museum Castello Ursino in Catania have been chosen as the site of experimentation

Electron beams produced by innovative photocathodes based on nanodiamond layers

The investigation of two different photocathodes (PCs) based on nanodiamond (ND) layers, irradiated by a KrF nanosecond excimer laser (wavelength, \ensuremath{\lambda}=248\text{ }\text{ }\mathrm{nm}; photon energy, ${E}_{\mathrm{Ph}}=5\text{ }\text{ }\mathrm{eV}$) is reported. The ND layers were deposited by means of a pulsed spray technique. Specifically, the active layer of each PC consisted of untreated (as-received) and hydrogenated ND particles, 250 nm in size, sprayed on a $p$-doped silicon substrate. The ND-based photocathodes were tested in a vacuum chamber at {10}^{\ensuremath{-}6}\text{ }\text{ }\mathrm{mbar} and compared to a Cu-based one, used as reference. All the photocathodes were irradiated at normal incidence. The quantum efficiency (QE) of the photocathodes was assessed. QE values of the ND-based photocathodes were higher than that of the reference one. In particular, the hydrogenated ND-based PC exhibited the highest QE due to the negative electron affinity that results from the surface terminated by hydrogen. Additionally, the photocathode surface/local temperature and the multiphoton process contribution to the electron emission were studied

The interaction of native DNA with Zn(II) and Cu(II) complexes of 5-triethyl ammonium methyl salicylidene orto-phenylendiimine

The interaction of native calf thymus DNA with the Zn(II) and Cu(II) complexes of 5-triethyl ammonium methyl salicylidene ortophenylendiimine (ZnL2+ and CuL2+), in 1 mM Tris-HCl aqueous solutions at neutral pH, has been monitored as a function of the metal complex-DNA molar ratio by UV absorption spectro photometry, circular dichroism (CD) and fluorescence spectroscopy. The results support for an intercalative interaction of both ZnL2+ and CuL2+ with DNA, showing CuL2+ an affinity of approximately 10 times higher than ZnL2+. In particular, the values of the binding constant, determined by UV spectrophotometric titration, equal to 7.3 x 10(4) and 1.3 x 10(6) M-1. for ZnL2+ and CuL2+, respectively, indicate the occurrence of a marked interaction with a binding size of about 0.7 in base pairs. The temperature dependence of the absorbance at 258 nm suggests that both complexes strongly increase the DNA melting temperature (Tm) already at metal complex-DNA molar ratios equal to 0.1. As evidenced by the quenching of the fluorescence of ethidium bromide-DNA solutions in the presence of increasing amounts of metal complex, ZnL2+ and CuL2+ are able to displace the ethidium cation intercalated into DNA. A tight ZnL2+-DNA and CuL2+-DNA binding has been also proven by the appearance, in both metal complex-DNA solutions, of a broad induced CD band in the range 350-450 nm. In the case of the CuL2+-DNA system, the shape of the CD spectrum, at high CuL2+ content, is similar to that observed for psi-DNA solutions. Such result allowed us to hypothesize that CuL2+ induces the formation of supramolecular aggregates of DNA in aqueous solutions

Molecular dynamics of electrosprayed water nanodroplets containing sodium bis(2-ethylhexyl)sulfosuccinate

The behavior of aqueous solutions of sodium bis(2-ethylhexyl)sulfosuccinate (AOTNa) subject to electrospray ionization (ESI) has been investigated by molecular dynamics (MD) simulations at three temperatures (350, 500 and 800 K). We consider several types of water nanodroplets containing AOTNa molecules and composed of a fixed number of water molecules (1000), N0 AOT AOT anions (N0 AOT = 0, 5, 10) and N0 Na sodium ions (N0 Na = 0, 5, 10, 15, 20): in a short time scale (less than 1 ns), the AOTNa molecules, initially forming direct micelles in the interior of the water nanodroplets, are observed in all cases to diffuse nearby the nanodroplet surface, so that the hydrophilic heads and sodium ions become surrounded by water molecules, whereas the alkyl chains lay at the droplet surface. Meanwhile, evaporation of water molecules and of solvated sodium ions occurs, leading to a decrease of the droplet size and charge. At 350 K, no ejection of neutral or charged surfactant molecules is observed, whereas at 500 K, some fragmentation occurs, and at 800 K, this event becomes more frequent. The interplay of all these processes, which depend on the values of temperature, N0 AOT and N0 Na eventually leads to anhydrous charged surfactant aggregates with prevalence of monocharged ones, in agreement with experimental results of ESI mass spectrometry. The quantitative analysis of theMD trajectories allows to evidencemolecular details potentially useful in designing future ESI experimental conditions

Inclusion complexes of cyclomaltooligosaccharides (cyclodextrins) with melatonin in solid phase

Fourier transform infrared spectrometry (FT-IR) and X-Ray diffraction (XRD) investigations were carried out on MLT plus α-, β- and γ-CD physical mixtures and lyophilized or crystalline MLT/α-, β-, γ-CD complexes. Inclusion complexes formation between MLT and cyclodextrins in solid phase has been emphasized by the significant differences between IR and XRD spectra of physical mixtures with respect to those of the complexes. The structure of MLT CDs complexes in the solid state as well as the biochemical and pharmaceutical implications are discussed

Acute appendicitis in infants

Acute appendicitis is very uncommon in the first year of life and often its presentation is atypical with high risk of complications. Hereby, we present 4 clinical cases of infants, who were diag- nosed with acute appendicitis in our hospital over the last year. The reported clinical cases high- light the several drawbacks clinicians face when managing infants with symptoms suggestive for acute appendicitis. After specific diagnostic work-up, even if not conclusive, patients were intra- operatively diagnosed with acute appendicitis and underwent appendicectomy. Maintaining a high index of suspicion for acute appendicitis in infants presenting with intra-abdominal sepsis of unclear etiology is, in our opinion, the most crucial factor to avoid complications and longer hospitalization