Dependence of the surface roughness of MAPLE-deposited films on the solvent parameters

Matrix-assisted pulsed laser evaporation (MAPLE) was used to deposit layers of poly(9,9-dioctylfluorene) (PFO) to study the relation between the solvent properties (laser light absorption, boiling temperature and solubility parameters) and the morphology of the deposited films. To this end, the polymer was diluted (0.5 wt%) in tetrahydrofuran—THF, toluene and toluene/hexane mixtures. The thickness of the films was equal to 70±20 nm. The morphology and uniformity of the films was investigated by Atomic Force Microscopy and by the photoluminescence emission properties of the polymer films, respectively. It is shown that, although the solubility parameters of the solvents are important in controlling the film roughness and morphology, the optical absorption properties and boiling temperature play a very important role, too. In fact, for matrices characterized by the same total solubility parameter, lower roughness values are obtained for films prepared using solvents with lower penetration depth of the laser radiation and higher boiling temperatures.     

Analysis of epoxyeicosatrienoic acids by chiral liquid chromatography/electron capture atmospheric pressure chemical ionization mass spectrometry using [13C]-analog internal standards

The metabolism of arachidonic acid (AA) to epoxyeicosatrienoic acids (EETs) is thought to be mediated primarily by the cytochromes P450 (P450s) from the 2 family (2C9, 2C19, 2D6, and 2J2). In contrast, P450s of the 4 family are primarily involved in omega oxidation of AA (4A11 and 4A22). The ability to determine enantioselective formation of the regioisomeric EETs is important in order to establish their potential biological activities and to asses which P450 isoforms are involved in their formation. It has been extremely difficult to analyze individual EET enantiomers in biological fluids because they are present in only trace amounts and they are extremely difficult to separate from each other. In addition, the deuterium-labeled internal standards that are commonly used for stable isotope dilution liquid chromatography/mass spectrometry (LC/MS) analyses have different LC retention times when compared with the corresponding protium forms. Therefore, quantification by LC/MS-based methodology can be compromised by differential suppression of ionization of the closely eluting isomers. We report the preparation of [(13)C(20)]-EET analog internal standards and the use of a validated high-sensitivity chiral LC/electron capture atmospheric pressure chemical ionization (ECAPCI)-MS method for the trace analysis of endogenous EETs as their pentafluorobenzyl (PFB) ester derivatives. The assay was then used to show the exquisite enantioselectivity of P4502C19-, P4502D6-, P4501A1-, and P4501B1-mediated conversion of AA into EETs and to quantify the enantioselective formation of EETs produced by AA metabolism in a mouse epithelial hepatoma (Hepa) cell line.     

Condensation of substituted 2-aminopyridine with β-ketocarboxylic esters: 4H-pyrido[1,2-a]pyrimidin-4-ones and pyridin-2-ones

We report the condensation of substituted 2-aminopyridines 5 with β-ketocarboxylic esters in polyphosphoric acid. In this reaction were obtained together with the target compounds, 4H-pyrido[1,2-a]pyrirnidin-4-ones 6 also the pyridin-2-ones 7 . All the compounds 7 were tested for their calcium-antagonistic activity but failed to evoke any vasorelaxant response.     

Anti-Inflammatory Activity of a CB2 Selective Cannabinoid Receptor Agonist: Signaling and Cytokines Release in Blood Mononuclear Cells

The endocannabinoid system (ECS) exerts immunosuppressive effects, which are mostly mediated by cannabinoid receptor 2 (CBR2), whose expression on leukocytes is higher than CBR1, mainly localized in the brain. Targeted CBR2 activation could limit inflammation, avoiding CBR1-related psychoactive effects. Herein, we evaluated in vitro the biological activity of a novel, selective and high-affinity CBR2 agonist, called JT11, studying its potential CBR2-mediated anti-inflammatory effect. Trypan Blue and MTT assays were used to test the cytotoxic and anti-proliferative effect of JT11 in Jurkat cells. Its pro-apoptotic activity was investigated analyzing both cell cycle and poly PARP cleavage. Finally, we evaluated its impact on LPS-induced ERK1/2 and NF-kB-p65 activation, TNF-α, IL-1β, IL-6 and IL-8 release in peripheral blood mononuclear cells (PBMCs) from healthy donors. Selective CB2R antagonist SR144528 and CBR2 knockdown were used to further verify the selectivity of JT11. We confirmed selective CBR2 activation by JT11. JT11 regulated cell viability and proliferation through a CBR2-dependent mechanism in Jurkat cells, exhibiting a mild pro-apoptotic activity. Finally, it reduced LPS-induced ERK1/2 and NF-kB-p65 phosphorylation and pro-inflammatory cytokines release in human PBMCs, proving to possess in vitro anti-inflammatory properties. JT11 as CBR2 ligands could enhance ECS immunoregulatory activity and our results support the view that therapeutic strategies targeting CBR2 signaling could be promising for the treatment of chronic inflammatory diseases.     

Catalysis of the water gas shift reaction by cis -[Rh(CO)2(AMINE)2](PF6) complexes in an aqueous tetrabutylammonium hydrogensulfate solution

Rhodium(I) complexes, cis-[Rh(CO)₂(amine)₂](PF₆) (amine = 4-picoline, 3-picoline, 2-picoline, pyridine, 3,5-lutidine or 2,6-lutidine) dissolved in an aqueous solution of tetrabutylammonium hydrogensulfate (N(C₄H₉)₄HSO₄), catalyze the water-gas shift reaction (WGSR). The role of the coordinated amine on the catalytic activity was examined.     

Uniform thin films of TiO2 nanoparticles deposited by matrix-assisted pulsed laser evaporation

We report morphological and optical properties of a colloidal TiO₂ nanoparticle film, deposited on a quartz substrate by using the Matrix-Assisted Pulsed Laser Evaporation (MAPLE) technique. Atomic Force Microscopy demonstrated that a good uniformity of the deposition can be obtained. The presence of agglomerates with dimensions of about 1 μm in size was noticed. Form UV-vis transmission spectra, recorded in the 200-800 nm range, the optical constants and the energy gap were determined besides the film thickness. The optical constants resulted in agreement with the values reported in literature for TiO₂ nanoparticle thin films.     

Three-dimensional flow pattern visualization and bubble size distributions in stationary and transient upward flashing flow

For the first time, an experimental three-dimensional reconstruction and visualization of stationary and transient flashing flow in a vertical pipe (47 mm diameter) is presented. The measurements have been performed by means of wire-mesh sensors. This type of sensor delivers two-dimensional void-fraction distributions in the pipe cross-section where it is mounted with a maximum sampling rate of 10,000 frames per second. A sampling rate of 1200 frames per second has been used in this work. Steam bubbles have been identified from the wire-mesh data and their complete three-dimensional reconstruction has been performed by taking into account the steam bubble velocity. For the estimation of the bubble velocity, two wire-mesh sensors positioned at a small axial distance from each other have been used. The velocity has been determined by cross-correlation of the two wire-mesh signals, by direct identification of the traveling time of the steam bubbles between the two sensors and by means of a drift-flux model. A comparison between the three methods of bubbles velocity measurement is reported. Stationary and time-dependent bubble size distributions have been derived. The stationary radial void-fraction profiles have been decomposed according to bubble size classes and compared with the results obtained with an equilibrium model.     

A Bifunctional Amorphous Polymer Exhibiting Equal Linear and Circular Photoinduced Birefringences

The large and reversible photoinduced linear and circular birefringences in azo‐compounds are at the basis of the interest in these materials, which are potentially useful for several applications. Since the onset of the linear and circular anisotropies relies on orientational processes, which typically occur on the molecular and supramolecular length scale, respectively, a circular birefringence at least one order of magnitude lower than the linear one is usually observed. Here, the synthesis and characterization of an amorphous polymer with a dimeric repeating unit containing a cyanoazobenzene and a cyanobiphenyl moiety are reported, in which identical optical linear and circular birefringences are induced for proper light dose and ellipticity. A pump‐probe technique and an analytical method based on the Stokes–Mueller formalism are used to investigate the photoinduced effects and to evaluate the anisotropies. The peculiar photoresponse of the polymer makes it a good candidate for applications in smart functional devices.