Assessment of the negative factors responsible for the decrease in the enantioselectivity for the ring opening of epoxides catalyzed by chiral supported Cr(III)-salen complexes

In order to determine the influence of the inorganic support on the asymmetric induction, different chiral chromium(III)-salen complexes have been incorporated within the cavities of zeolites Y, EMT and into the interlamellar region of K-10 montmorillonite. These heterogeneous catalysts are able to promote the asymmetric ring opening of epoxides with trimethylsilylazide to afford chiral azido trimethylsilyl ethers and azido alcohols with modest enantiomeric excess that varies depending on the inorganic support. The factors that have been found to play a negative influence diminishing the enantioselectivity of the supported Cr(III)-salen catalyst compared to the unsupported complexes are the following: (i) the presence of adventitious acid sites, (ii) the encapsulation of no sufficiently stereogenic ligands and (iii) the change in the reaction mechanism from bimetallic to a single metal reaction mechanism. This revised version was published online in July 2006 with corrections to the Cover Date.     

Continuous catalyst-free methanolysis and ethanolysis of soybean oil under supercritical alcohol/water mixtures

This work investigates and compares the reaction performance of soybean oil transesterification under supercritical methanol and ethanol, in a continuous catalyst-free process, as a cleaner alternative to conventional chemically catalyzed process. Reactions were performed in a tubular reactor, at 20 MPa, with oil to alcohol ratio of 1:40, varying the temperature in the range from 250 °C to 350 °C, and at two levels of water concentrations, 0 and 10 wt%. Although both processes proceeded with a relatively high reaction rate, conversion achieved by methanolysis was higher than that obtained by ethanolysis. Water positively affected both process: higher ester content and triacylglycerols depletion occurred when 10 wt% water was used compared with anhydrous conditions. Temperature increase favored the conversion of soybean oil to the corresponding methyl or ethyl esters, although temperatures above 300 °C increased the fatty acid degradation degree, a phenomenon responsible for the low ester contents obtained at the highest temperatures and lowest flow rates studied.     

Microstructural study of aged ferrite powders for sensing layers

Nanosized powders of La_0.80Sr_0.20Fe_0.95Cu_0.05O_3?w were investigated in terms of structural, morphological, chemical and surface properties by using several characterization techniques. The XPS and IR measurements showed the presence of surface hydroxide and carbonates species. After calcination of the powders at 900 °C the amount of carbonates decreased but was still significant. The sensing activity of thick film based on La_0.80Sr_0.20Fe_0.95Cu_0.05O_3?w was tested as a function of relative humidity and the results indicate that (i) after one year of ambient storage the sensing material lost quite completely its sensitivity to humidity, (ii) the sensing activity of the film was mostly re-activated after a thermal treatment at 900 °C for 2 h, and (iii) the huge shift of the detection limit to low RH caused by the presence of 5 mol% Cu is also restored.     

A Simple and Effective Mass Spectrometric Approach to Identify the Adulteration of the Mediterranean Diet Component Extra-Virgin Olive Oil with Corn Oil

Extra virgin olive oil (EVOO) with its nutraceutical characteristics substantially contributes as a major nutrient to the health benefit of the Mediterranean diet. Unfortunately, the adulteration of EVOO with less expensive oils (e.g., peanut and corn oils), has become one of the biggest source of agricultural fraud in the European Union, with important health implications for consumers, mainly due to the introduction of seed oil-derived allergens causing, especially in children, severe food allergy phenomena. In this regard, revealing adulterations of EVOO is of fundamental importance for health care and prevention reasons, especially in children. To this aim, effective analytical methods to assess EVOO purity are necessary. Here, we propose a simple, rapid, robust and very sensitive method for non-specialized mass spectrometric laboratory, based on the matrix-assisted laser desorption/ionization mass spectrometry (MALDI-TOF MS) coupled to unsupervised hierarchical clustering (UHC), principal component (PCA) and Pearson’s correlation analyses, to reveal corn oil (CO) adulterations in EVOO at very low levels (down to 0.5%).     

Validation of a UV Spectrophotometric Method for Determination of Proteolytic Activity of Enzymatic Detergents

Enzymatic detergents are widely used in health services. These products should be controlled to ensure their activity. In this paper, a UV spectrophotometric method for the determination of proteolytic activity in enzymatic detergents was validated. An artificial substrate (azocasein) was used to quantify the enzyme activity at 340 nm. The results showed that the method was satisfactory in respect to its specificity, linearity, precision, accuracy and robustness. This method fulfills both ICH’s and Brazilian criteria, demonstrating its suitability for routine analysis as well as its potential application for regulatory purposes.     

Transforming shortcomings into opportunities: Can market incentives solve Lebanon's energy crisis?

Over the past decades Lebanon's energy sector has been largely ignored and this has led to high economic and environmental costs. The sector is characterized by electricity poverty, an expanding and mainly unregulated transport sector and a lack of energy savings spanning through all sectors of the economy. Recently, the Government of Lebanon has committed to increase the share of renewable energy to 10% of the total energy supply by 2013 and to 12% by the year 2020; it also aims at reducing energy consumption by 6% by the year 2013. This paper aims at contributing to the formulation of a more comprehensive energy strategy for Lebanon by analyzing the recent changes in policy direction and by recommending legal, regulatory and policy measures in order to transform current shortcomings into opportunities allowing the country to become a regional ‘success story’ in the deployment of renewable energy and energy efficiency.     

Non-Standard Semantics for Program Slicing

In this paper we generalize the notion of compositional semantics to cope with transfinite reductions of a transition system. Standard denotational and predicate transformer semantics, even though compositional, provide inadequate models for some known program manipulation techniques. We are interested in the systematic design of extended compositional semantics, observing possible transfinite computations, i.e. computations that may occur after a given number of infinite loops. This generalization is necessary to deal with program manipulation techniques modifying the termination status of programs, such as program slicing. We include the transfinite generalization of semantics in the hierarchy developed in 1997 by P. Cousot, where semantics at different levels of abstraction are related with each other by abstract interpretation. We prove that a specular hierarchy of non-standard semantics modeling transfinite computations of programs can be specifiedin such a way that the standard hierarchy can be derived by abstract interpretation. We prove that non-standard transfinite denotational and predicate transformer semantics can be both systematically derived as solutions of simple abstract domain equations involving the basic operation of reduced power of abstract domains. This allows us to prove the optimality of these semantics, i.e. they are the most abstract semantics in the hierarchy which are compositional and observe respectively the terminating and initial states of transfinite computations, providing an adequate mathematical model for program manipulation.     

Temperature Tunable 4D Polymeric Photonic Crystals

Photonic crystals owe their multitude of optical properties to the way their structure creates interference effects. It is therefore possible to influence the photonic response by acting on their physical structure. In this article, tunable photonic crystals made by elastic polymers that respond to their environment are explored, in particular with a physical deformation under temperature variation. This creates a feedback process in which the photonic response depends on its physical structure, which itself is influenced by the environmental changes. By using a multi-photon polymerization process specifically optimized for soft responsive polymers such as Liquid Crystalline Networks, highly resolved, reproducible, and mechanically self-standing photonic crystals are fabricated. The physical structure of the 3D woodpile can be tuned by an external temperature variation creating a reversible spectral tuning of 50 nm in the telecom wavelength range. By comparing these results with finite element calculations and temperature induced shape-change, it is confirmed that the observed tuning is due to an elastic deformation of the structure. The achieved nanometric patterning of tunable anisotropic photonic materials will further foster the development of reconfigurable photonic crystals with point defects acting as tunable resonant cavities and, more in general, of 4D nanostructures.