Synthesis of sulfated galactocerebrosides from an orthogonal beta-D-galactosylceramide scaffold for the study of CD1-antigen interactions

CD1a protein binds sulfatide (3-O-sulfo-beta-D-galactosylceramide) to form an antigen complex that interacts with T cell receptors and activates T cells. To assess the role of the position of the sulfate in T cell activation, the synthesis of three beta-D-galactosylceramides, variously bearing a sulfate at position 2, 4, or 6 of galactose, has been planned and carried out. The compounds were synthesized by an orthogonal sulfation strategy from a common beta-D-galactosylceramide scaffold, which was in turn obtained through an efficient glycosylation reaction between a fully orthogonally protected galactosyl imidate and 3-O-benzoylazidosphingosine. Immunological evaluation of the three sulfated compounds in CD1a-mediated T cell activation, in comparison with natural sulfatide, provided evidence of the influence of the sulfate position in the recognition event between the antigen, the CD1 protein and the T cell receptor.     

Relevance of electron transfer mechanism in electrocatalysis: the reduction of organic halides at silver electrodes

The mechanism of dissociative electron transfer (ET) to a series of organic chlorides has been investigated both at an inert electrode and at a catalytic surface such as Ag; electrocatalysis is important only when breaking of the carbon-halogen bond is concerted with the ET.     

Comparison of different calibration methods for the determination by FT-NIR spectroscopy of the hydroxyl number in polyester resins

Different calibration methods have been applied for the determination of the Hydroxyl Number in polyester resins, namely Partial Least Squares (PLS), Principal Component Regression (PCR), Ordinary Least Squares with selection of the variables by genetic algorithm (OLS-GEN) and back-propagation Artificial Neural Networks (BP-ANN). The predictive ability of the regression models was estimated by splitting the dataset in training and test sets by application of the Kohonen self-organising maps. The linear methods (OLS-GEN, PLS and PCR) showed comparable results while artificial neural networks provided the best results both in fitting and prediction.     

Effect of compatibilization on thermal degradation kinetics of HDPE-based composites containing cellulose reinforcements

Dynamic thermogravimetric analysis under nitrogen flow was used to investigate the thermal decomposition process of high-density poly(ethylene) (HDPE)-based composites reinforced with cellulose fibers obtained from the recycling of multilayer carton scraps, as a function of the cellulose content and the compatibilization. The Friedman, Flynn–Wall–Ozawa, and Coats–Redfern methods were used to determine the apparent activation energy (E _a) of the thermal degradation of the cellulose component into the composites. E _a has been found dependent on the cellulose amount and on the cellulose/polymer matrix interfacial adhesion. In particular, it has been evidenced an increase of the cellulose thermal stability as a consequence of the improved interfacial adhesion between the components in NFR composites.     

Structure, resolution and chiroptical analysis of stable lanthanide complexes of a pyridylphenylphosphinate triazacyclononane ligand

Lanthanide complexes of a pyridylphenylphosphinate ligand based on triazacyclononane form an isostructural series. The C(3)-symmetric Δ and Λ complexes of Eu and Tb are strongly emissive and can be resolved by chiral HPLC; the absolute configuration of each complex has been assigned using CD and CPL measurements.     

Ion Chromatography Determination of Heavy Metals in Airborne Particulate with Preconcentration and Large Volume Direct Injection

A flow injection analysis system with on-line enrichment was developed for simultaneous determination of trace levels of Cu²⁺, Ni²⁺, Zn²⁺, Co²⁺, Mn²⁺, Cd²⁺, Pb²⁺ and Fe³⁺, by high-performance ion chromatography (HPIC) with spectrophotometric detection. It is a highly sensitive and low cost alternative methodology. Ion Pac CS5A was used as the analytical column with eluent composition of sodium nitrate 160 mM and oxalic acid 36 mM. Quantification after post-column reaction with PAR allows detection limits between 0.5 and 5.0 ppb to be attained. The total analysis time is less than 30 min. The proposed procedure was compared with a large volume direct injection method using loop volumes up to 5 mL. Both procedures were applied to the analysis of heavy metals in the PM10 fraction of atmospheric particulate samples. Airborne pollutants such as nickel and cobalt can be quantified in 24 h samples of particulate matter at concentrations of a few ng m^?3.     

Insights About CHAPS Aggregation Obtained by Spin Label EPR Spectroscopy

CHAPS is a zwitterionic surfactant derivative of bile salts, widely used in membrane protein isolation. While some studies regarding CHAPS self-aggregation suggest continuous increase in micelle size at increasing CHAPS concentration, other works point to the existence of two definite micelle types. In this work, stearic acid spin labels (5, 12, or 16-SASL) were added to CHAPS solutions to obtain information about the micellar structure using electron paramagnetic resonance spectroscopy. The spectra of 12-SASL were processed using Principal Factor Analysis, and at all concentrations they could be reproduced as linear combinations of only three fundamental spectra, the first one corresponding to free 12-SASL in aqueous solution. This fact suggests only two hydrophobic environments that host 12-SASL, assigned to primary and secondary CHAPS micelles. The relative populations of the label in each environment were obtained as a function of CHAPS concentration. Our results suggest barrel-shaped primary micelles with a minimum mean radius of 1.46 nm, and a critical micelle concentration cmc_I = 4 mM. Secondary micelles are formed by aggregation of primary ones, with cmc_II = 10 mM. They have several elongated hydrophobic pockets, with similar dimensions for all aggregate sizes. Our results contribute to the understanding of the mechanism of interaction of chain amphiphiles with CHAPS micelles.     

Self detachment of free-standing porous silicon membranes in moderately doped n-type silicon

In this article we describe a reliable etching method to fabricate porous silicon free-standing membranes (FSMs) based on a self detachment of the porous layer in moderately doped n-type silicon substrates. We found that stable growth of smooth and straight pores is restricted to a narrow range of etching conditions and, unlike p-type substrates, the lift-off of the membrane is a self-limited process that does not require a large burst of current. The detachment of the porous membrane is independent of the structure of the already porosified layer, meaning that the average pore diameter can be tuned from nano to macro size within the same membrane. We also demonstrate that, despite their limited thickness, FSMs are quite robust and can sustained further processing. Thus, the etching receipt we are proposing here extends the range of sensors and filters that can be fabricated using porous silicon technology.     

On the minimization of quadratic functions with bilinear constraints via augmented Lagrangians

In the present paper, a new set of necessary and sufficient conditions is given for the regulator problem with plant stability in the presence of disturbances. Significant features of these conditions are the simplicity of their statement and the immediacy of their meaning in the context of the geometric approach. The proof is based on arguments which are extensions of those developed in Part 1 for the more restricted problem of disturbance localization by dynamic compensation with stability. The sufficiency of conditions is proved by a constructive procedure, which may be used as part of an actual regulator synthesis method.This research has been supported in part by MPI, Rome, Italy.