Stereoelective polymerization of β-butyrolactone

Racemic β-butyrolactone was polymerized using chiral initiators obtained from the reaction of organometallic derivatives (ZnEt₂, CdMe₂, AlEt₃) with R(−) 3,3 dimethyl-1,2 butanediol. With the zinc initiator, R(+) enantiomer is preferentially incorporated in the polymer chain with a stereoelectivity ratio r_R equal to 1.6. Crude polymer was fractionated into a crystalline, predominantly isotactic, part and an amorphous heterotactic part, both optically active. Sites of different stereospecificities, present in the initiator, are all active for the stereoelective polymerization. With the cadmium initiator, S(−) enantiomer is preferentially polymerized (r_s = 1.01), extending homosteric-antisteric rules previously established for thiiranes. Aluminium initiator leads to an homosteric process (r_R = 1.1). Chiroptical properties (o.r.d. and c.d.) of polymers prepared with zinc initiator show a predominance of R-configurational units, indicating that ring-opening occurs by O-acyl cleavage with retention of configuration.     

Densification of 8Y‐Tetragonal‐Stabilized Zirconia Optoceramics with Improved Optical Properties by Y Segregation

8% Yttria‐stabilized zironcia (8YSZ) transparent ceramics have a wide technological applications. Segregation of the Y around the grain boundaries is favored by slow heating rate. The optimized sintering parameters helped in obtaining transparent ceramics of 8YSZ with a high percentage of cubic phase in addition to the presence of tetragonal phase. HRTEM was used to verify the grain growth suppression and to observe the presence of the cubic phase. The presence of cubic phase has suppressed the grain growth, which increased the transparency in the visible and infrared region without the addition of dopants or by utilizing high pressure.     

Effects of LP-MOCVD prepared TiO2 thin films on the in vitro behavior of gingival fibroblasts

We report on the in vitro response of human gingival fibroblasts (HGF-1 cell line) to various thin films of titanium dioxide (TiO₂) deposited on titanium (Ti) substrates by low pressure metal-organic chemical vapor deposition (LP-MOCVD). The aim was to study the influence of film structural parameters on the cell behavior comparatively with a native-oxide covered titanium specimen, this objective being topical and interesting for materials applications in implantology. HGF-1 cells were cultured on three LP-MOCVD prepared thin films of TiO₂ differentiated by their thickness, roughness, transversal morphology, allotropic composition and wettability, and on a native-oxide covered Ti substrate. Besides traditional tests of cell viability and morphology, the biocompatibility of these materials was evaluated by fibronectin immunostaining, assessment of cell proliferation status and the zymographic evaluation of gelatinolytic activities specific to matrix metalloproteinases secreted by cells grown in contact with studied specimens. The analyzed surfaces proved to influence fibronectin fibril assembly, cell proliferation and capacity to degrade extracellular matrix without considerably affecting cell viability and morphology. The MOCVD of TiO₂ proved effective in positively modifying titanium surface for medical applications. Surface properties playing a crucial role for cell behavior were the wettability and, secondarily, the roughness, HGF-1 cells preferring a moderately rough and wettable TiO₂ coating.     

Multiresidue analysis of multiclass pesticides in lavandin essential oil by LC/MS/MS using the scheduled selected reaction monitoring mode

In this paper we describe the development of the first multiclass pesticide residue method applied to essential oils. A total of 70 pesticides covering a wide range of polarity and currently used on essential oil crops have been included in the method. The procedure consists of a 10-fold dilution of lavandin essential oil followed by a direct injection analysis by liquid chromatography/tandem mass spectrometry. The system used is an API 4000 QTrap equipped with an electrospray ionization interface and operating in scheduled selected reaction monitoring acquisition mode. Matrix effects were evaluated by comparing the slopes of matrix-matched and solvent-based calibration curves. Weak signal suppression or enhancement (<20%) was observed for most of the compounds. Method sensitivity was determined statistically by the injection of five matrix-matched calibration curves with the distribution's normality and the variance's homogeneity checked before establishment of a suitable regression model. Limits of detection (LODs) and quantification (LOQs) were then determined using the blank standard's deviation and the slope of the mean curve. The analytical method has been validated for 67 of the 70 pesticides and meets the following LOQs: ≤1 μg/L for 9 pesticides, ≤5 μg/L for 44, ≤10 μg/L for 9, and ≤20 μg/L for 5.     

Influence of the sampling area of the stem on the mechanical properties of hemp fibers

Natural fibers appear to be a promising alternative to glass fibers for the reinforcement of polymer matrix composites. However, the wide dispersion of their mechanical properties slows down their development.The aim of this study was to evaluate the influence of the sampling area of the stem on the mechanical properties of hemp fibers. Tensile tests were carried out on fibers extracted from the bottom, the middle, and the top of one stem. The results show there is only slight variations between the different areas: fibers from the middle exhibit higher tensile strength and ultimate elongation than top and bottom fibers, but there are no differences in terms of stiffness. A strong dependence of the fiber mechanical properties on their diameter is observed. This dependence induces more dispersion of the properties than the sampling area, thus it seems relevant to consider the whole stem to extract fibers, without defining distinct areas.     

Non-homogeneous extracellular resistivity affects the current-source density profiles of up-down state oscillations

Rhythmic local field potential (LFP) oscillations observed during deep sleep are the result of synchronized electrical activities of large neuronal ensembles, which consist of alternating periods of activity and silence, termed 'up' and 'down' states, respectively. Current-source density (CSD) analysis indicates that the up states of these slow oscillations are associated with current sources in superficial cortical layers and sinks in deep layers, while the down states display the opposite pattern of source-sink distribution. We show here that a network model of up and down states displays this CSD profile only if a frequency-filtering extracellular medium is assumed. When frequency filtering was modelled as inhomogeneous conductivity, this simple model had considerably more power in slow frequencies, resulting in significant differences in LFP and CSD profiles compared with the constant-resistivity model. These results suggest that the frequency-filtering properties of extracellular media may have important consequences for the interpretation of the results of CSD analysis.     

Amorphous alumina coatings: processing, structure and remarkable barrier properties

Amorphous aluminium oxide coatings were processed by metalorganic chemical vapour deposition (MOCVD); their structural characteristics were determined as a function of the processing conditions, the process was modelled considering appropriate chemical kinetic schemes, and the properties of the obtained material were investigated and were correlated with the nanostructure of the coatings. With increasing processing temperature in the range 350 degrees C-700 degrees C, subatmospheric MOCVD of alumina from aluminium tri-isopropoxide (ATI) sequentially yields partially hydroxylated amorphous aluminium oxides, amorphous Al2O3 (415 degrees C-650 degrees C) and nanostructured gamma-Al2O3 films. A numerical model for the process allowed reproducing the non uniformity of deposition rate along the substrate zone due to the depletion of ATI. The hardness of the coatings prepared at 350 degrees C, 480 degrees C and 700 degrees C is 6 GPa, 11 GPa and 1 GPa, respectively. Scratch tests on films grown on TA6V titanium alloy reveal adhesive and cohesive failures for the amorphous and nanocrystalline ones, respectively. Alumina coating processed at 480 degrees C on TA6V yielded zero weight gain after oxidation at 600 degrees C in lab air. The surface of such low temperature processed amorphous films is hydrophobic (water contact angle 106 degrees), while the high temperature processed nanocrystalline films are hydrophilic (48 degrees at a deposition temperature of 700 degrees C). It is concluded that amorphous Al2O3 coatings can be used as oxidation and corrosion barriers at ambient or moderate temperature. Nanostructured with Pt or Ag nanoparticles, they can also provide anti-fouling or catalytic surfaces.     

Simultaneous heat and mass transfer in a packed binary distillation column

A simultaneous heat and mass transfer model was applied to a binary system in a 3-in. distillation column packed with $\text{1}\text{4}$in. Raschig Rings. MaThe experiments carried out with the toluene-trichloroethylene system show that the liquid phase is saturated, indicating no resistance to mass transfe