Numerical differentiation on scattered data through multivariate polynomial interpolation

BIT Numerical Mathematics - We discuss a pointwise numerical differentiation formula on multivariate scattered data, based on the coefficients of local polynomial interpolation at Discrete Leja...     

Enantioselective enzymatic resolution of racemic alcohols by lipases in green organic solvents

The effects of two eco-friendly solvents, 2-methyltetrahydrofuran (MeTHF) and cyclopentyl methyl ether (CPME), on the enzyme activity and enantioselectivity of Novozym 435, Candida rugosa lipase (CRL), Porcine pancreas lipase (PPL), Lipase AK, Lipase PS, and Lipozyme, a series of commercial lipases, in the enantioselective transesterfications of racemic menthol, racemic sulcatol and racemic α-cyclogeraniol were studied. Vinyl acetate was chosen as the acyl donor and the reactions were carried out at water activity 0.06. The activity of lipases in CPME was similar to that observed in other largely employed organic solvents [toluene and tert-butyl methyl ether (MTBE)], and was slightly lower in MeTHF. However, for most of the lipases tested, the enantioselectivity was higher in the eco-friendly solvents. Lipase AK exhibited a high enantioselectivity (E = 232) for the resolution of racemic menthol but the reaction rate was low. Lipase formulation (the enzyme was frozen and lyophilized in potassium phosphate buffer without and with 5% (w/v) of sucrose, d-mannitol, or methoxy poly(ethylene glycol)) was tested with this lipase in order to improve its activity, which increased up to 4.5 times, compared to the untreated enzyme. CALB was found to be a useful biocatalyst for the resolution of racemic sulcatol, where high activity and enantioselectivity were obtained (E ≥ 1000). For the resolution of the racemic primary alcohol α-cyclogeraniol, most of the lipases tested were active but not enantioselective, except lipase PS which displayed a moderate enantioselectivity (E = 19). The effect of the presence of a low percentage of two ionic liquids (ILs) 1-Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM][TFSI]) (5% (v/v)) and 1-Butyl-3-methylimidazoliumtetrafluoroborate ([BMIM][BF4]) (1% (v/v)) in the medium was also investigated. Only in the case of CRL the ILs slightly increased the enantioselectivity from E = 91 to E = 103 and E = 120 for [BMIM][TFSI] and [BMIM][BF4], respectively. However, in all cases ILs caused a decrease of enzyme activity.     

Sonochemical Formation of Iodohydrin and Epoxide from Cyclohexene

Ultrasonic irradiation substantially improves the reaction of cyclohexene with I₂ in aqueous dioxane in the presence of Cu(OAc)₂ · H₂O to generate the expected iodohydrin in high yield. The product undergoes cyclization to the epoxide by biphasic treatment with either Na₂CO₃ or KOH in a sonication‐sensitive step.     

Synthesis of bifunctional cyclic carbonates from CO2 catalysed by choline-based systems

Easily prepared choline iodide is an active catalyst for the synthesis of cyclic carbonates through the coupling reaction of CO₂ and epoxides using low pressure (1 MPa), moderate temperature (85 ºC) and green solvents (ethanol and propan-2-ol). The effects of reaction temperature, pressure, reaction time and amount of catalyst used were also investigated. The results showed moderate to high yields and excellent selectivities of cyclic carbonates with vinyl or acrylate groups under mild reaction conditions. The heterogenization of choline over a Merrifield resin gives access to a supported catalyst with good recyclability and reactivity that can be extended to a variety of terminal epoxide substrates.     

A New Cells‐Compatible Microfluidic Device for Single Channel Recordings

We report the fabrication of a microfluidic apparatus and the realization of a sensors based on PEDOT : PSS, a biocompatible semiconductor polymer used in substitution of standard electrodes for electrophysiological studies and for detection of nanopores in membrane. This gives the possibility to study the mechanisms of ions balance and molecular transport though cell membranes. In particular the apparatus is based on two chambers connected through an aperture in a PTFE sheet where lipid bilayer are formed using Montal‐Mueller method, and the pore‐forming proteins activity is detected by polymeric electrodes. This methodology could be applied to examine different membrane proteins for the purpose of biosensing, drug screening and nanopore technologies.     

Probing Substrate/Catalyst Effects Using QSPR Analysis on Friedel-Crafts Acylation Reactions over Hierarchical BEA Zeolites

Attempts to optimize heterogeneous catalysis often lack quantitative comparative analysis. The use of kinetic modelling leads to rate (k) and relative sorption equilibrium constants (K), which can be further rationalized using Quantitative Structure-Property Relationships (QSPR) based on Multiple Linear Regressions (MLR). Friedel-Crafts acylation using commercial and hierarchical BEA zeolites as heterogeneous catalysts, acetic anhydride as the acylating agent, and a set of seven substrates with different sizes and chemical functionalities were herein studied. Catalytic results were correlated with the physicochemical properties of substrates and catalysts. From this analysis, a robust set of equations was obtained allowing inferences about the dominant factors governing the processes. Not entirely surprising, the rate and sorption equilibrium constants were found to be explained in part by common factors but of opposite signs: higher and stronger adsorption forces increase reaction rates, but they also make the zeolite active sites less accessible to new reactant molecules. The most relevant parameters are related to the substrates’ molecular size, which can be associated with different reaction steps, namely accessibility to micropores, diffusion capacity, and polarizability of molecules. The relatively large set of substrates used here reinforces previous findings and brings further insights into the factors that hamper/speed up Friedel-Crafts reactions in heterogeneous media.     

Topological properties of commodities networks

This paper investigates the topological properties of the commodities networks. We have found that commodities form strong clusters and are homogeneous with relation to sector (metals, agriculture and energy). We also develop a dynamic approach suggesting that agriculture commodities are very important in the network, followed by metals and energy. Furthermore, the parameters that characterize the network seem to be changing over time.     

Generic-Type Results for Chaotic Dynamics in Equations with Periodic Forcing Terms

We prove that a class of equations containing the classical periodically forced pendulum problem displays the main features of chaotic dynamics for a set of forcing terms open and dense in suitable spaces. The approach is based on global variational methods.     

Polysialylated-neural cell adhesion molecule (PSA-NCAM) in the human trigeminal ganglion and brainstem at prenatal and adult ages

Background  

The polysialylated neuronal cell adhesion molecule (PSA-NCAM) is considered a marker of developing and migrating neurons and of synaptogenesis in the immature vertebrate nervous system. However, it persists in the mature normal brain in some regions which retain a capability for morphofunctional reorganization throughout life. With the aim of providing information relevant to the potential for dynamic changes of specific neuronal populations in man, this study analyses the immunohistochemical occurrence of PSA-NCAM in the human trigeminal ganglion (TG) and brainstem neuronal populations at prenatal and adult age.