Structural effects on the acidity of E-α-phenyl-β-arylacrylic acids

The dissociation equilibrium constants of some is-α-phenyl-β-arylacrylic acids (Ar = 2-pyridyl, 3-pyridyl, 4-pyridyl, 1-naphthyl, 2-naphthyl, anthracen-9-yl) have been measured in 80% aqueous 2-methoxyethanol at 25°. The pKa values of these acids, together with those of p-substituted phenyl, 2-furyl, 2-thienyl and selenophen-2-yl derivatives, have been rationalized by an equation involving separate contributions of polar, conjugative and steric effects of heterocycles. The pKa values of some E-α-phenyl-β-alkylacrylic acids (alk = methyl; ethyl; n-propyl; i-propyl; n-butyl; i-butyl) are also reported.     

Speciation of heavy metals in sediments of the lagoon of Venice collected in the industrial area

In this study a procedure of sequential extraction of metals from sediments was applied to samples from the lagoon of Venice. Compared to the measurement of total concentrations, the knowledge of metal partitioning among sediment phases can help in estimating the risk posed by metal polluted sediments and give information on contamination sources and on the factors that influence metal enrichment in sediments. The results permitted to estimate for each metal the percentage of the total content that could be potentially remobilized from sediments, owing to changes in environmental conditions. The immediately available fraction represented in general a low proportion of the total content. An important proportion of most metals (except for Zn, Cd and Cu) was associated to residual phases and therefore was not expected to be released under the normal environmental conditions. The large amounts of metals bound to Fe-Mn oxides/hydroxides confirmed the strong scavenging efficiency of this phase. The carbonate phase was the preferential associative form for Pb, Cd and Zn, whereas Cu was bound in prevalence to the organic matter/sulphide phase.     

Quantum monte carlo methods for constrained systems

The torsional ground state for ethane, the torsional, rotational, and mixed torsional and rotational ground state of propane are computed with a version of diffusion Monte Carlo adapted to handle the geometric complexity of curved spaces such as the Ramachandra space. The quantum NVT ensemble average for the mixed torsional and rotational degrees of freedom of propane is computed, using a version of Monte Carlo path integral, also adapted to handle curved spaces. These three problems are selected to demonstrate the generality and the applicability of the approaches described. The spaces of coordinates can be best constructed from the parameters of continuous Lie groups, and alternative methods based on vector spaces, where extended Lagrangian terms would be too cumbersome to implement. We note that the geometric coupling between the torsions and the rotations of propane produces a substantial effect on the ground state energy of propane, and that the quantum effects on the energy of propane are quite large even well above room temperature. © 2014 Wiley Periodicals, Inc.     

Steric course of some cyclopropanation reactions of L-threo-hex-4-enopyranosides

Completely protected 4-deoxy-α-L-threo-hex-4-enopyranosides 1c,d undergo the dichlorocarbene addition affording exclusively diastereomeric adducts 5c,d with the cyclopropane ring anti to the C-3 alkyloxy substituent, while the reaction with 3-unprotected derivatives 1a,b affords a mixture of syn and anti derivatives. Under the Simmons-Smith cyclopropanation adducts 2a-d with a syn stereochemistry are obtained. Starting from 5b, the cyclopropanated sugar 3b is obtained by reduction with LiAlH₄, thus the two diastereomers 2b and 3b can be stereoselectively obtained through the two different pathways. For a useful comparison, 4-deoxy-β-L-threo-hex-4-enopyranoside 1e was also subjected to the above two cyclopropanation methods affording the expected cycloadduct 2e and a diastereomeric mixture of dichlorocycloadducts 4e and 5e (4e/5e=2.8:1).     

Pulling direction as a reaction coordinate for the mechanical unfolding of single molecules

The folding and unfolding kinetics of single molecules, such as proteins or nucleic acids, can be explored by mechanical pulling experiments. Determining intrinsic kinetic information, at zero stretching force, usually requires an extrapolation by fitting a theoretical model. Here, we apply a recent theoretical approach describing molecular rupture in the presence of force to unfolding kinetic data obtained from coarse-grained simulations of ubiquitin. Unfolding rates calculated from simulations over a broad range of stretching forces, for different pulling directions, reveal a remarkable "turnover" from a force-independent process at low force to a force-dependent process at high force, akin to the "roll-over" in unfolding rates sometimes seen in studies using chemical denaturant. While such a turnover in rates is unexpected in one dimension, we demonstrate that it can occur for dynamics in just two dimensions. We relate the turnover to the quality of the pulling direction as a reaction coordinate for the intrinsic folding mechanism. A novel pulling direction, designed to be the most relevant to the intrinsic folding pathway, results in the smallest turnover. Our results are in accord with protein engineering experiments and simulations which indicate that the unfolding mechanism at high force can differ from the intrinsic mechanism. The apparent similarity between extrapolated and intrinsic rates in experiments, unexpected for different unfolding barriers, can be explained if the turnover occurs at low forces.     

Interdonato lemon from Nizza di Sicilia (Italy): chemical composition of hexane extract of lemon peel and histochemical investigation

Considering that the determination of authenticity and of the geographical origin of food is a very challenging issue, in this study we studied by means of histological and histochemical analyses the famous Sicilian lemon known as ‘Interdonato Lemon of Messina PGI’. Since the protected geographical indication Interdonato lemon of Messina possesses high organoleptic properties, the composition of the hexane extract of lemon peel was determined by HRGC and HRGC–MS analyses and compared with that of lemon of different cultivars. The results obtained are informative of the oil’s quality and explain the variation of the lemon essential oil composition. Given the fundamental economic implications of any fraud, the aim of this study was to determine a fingerprint able to evaluate the authentication of the geographic origin in such way to prevent frauds in national and international markets.     

Rheological Study on Polypropylene/Cycloolefin Copolymer Blends

Summary: Polypropylene, cycloolefin copolymer and their blends were characterized by means of melt flow analysis and capillary rheometry at temperatures between 190 and 230 °C in order to shed more light on COC fiber formation obtained in injection molding process. Melt viscosity and its activation energy as functions of blend composition show negative deviation from the expected additivity (Negative Deviating Blends). The COC/PP viscosity ratio increases with shear rate, but decreases with temperature. High temperature, low viscosity ratio and high shear rate seem to be favorable for fiber formation. Glass transition (from the reversible heat flow curve of modulated DSC) of dumbbell specimens produced by injection molding at 230 °C with COC minor component was 2–4 °C higher than that of grinded pellets obtained from mixing at 190 °C.     

Time-programmable pH: decarboxylation of nitroacetic acid allows the time-controlled rising of pH to a definite value

In this report it is shown that nitroacetic acid 1 (O₂NCH₂CO₂H) can be conveniently used to control the pH of a water solution over time. Time-programmable sequences of the kind pH_1(high)–pH_2(low)–pH_3(high) can be achieved, where both the extent of the initial pH jump (pH_1(high)–pH_2(low)) and the time required for the subsequent pH rising (pH_2(low)–pH_3(high)) can be predictably controlled by a judicious choice of the absolute and relative concentrations of the reagents (acid 1 and NaOH). Successive pH_1(high)–pH_2(low)–pH_3(high) sequences can be obtained by subsequent additions of acid 1. As a proof of concept, the method is applied to control over time the pH-dependent host–guest interaction between alpha-cyclodextrin and p-aminobenzoic acid.

Predictable and time-programmable sequences of the kind pH_1(high)–pH_2(low)–pH_3(high) in water solution are obtained by a judicious choice of the concentration of nitroacetic acid undergoing decarboxylation.     

HPLC‐ESI‐MS analysis of oral human fluids reveals that gingival crevicular fluid is the main source of oral thymosins β4 and β10

Thymosin β₄ (Tβ₄), its sulfoxide, and thymosin β₁₀ (Tβ₁₀) were detected in human saliva and identified by different strategies based on RP HPLC coupled to electrospray multidimensional IT MS. Tβ₄ was almost always detected in whole saliva, its sulfoxide sporadically, Tβ₁₀ rarely. Tβ₄ was undetectable in parotid saliva and less concentrated in submandibular/sublingual saliva than in whole saliva. Analysis of gingival crevicular fluid revealed high relative amounts of Tβ₄, Tβ₄ sulfoxide, and Tβ₁₀ in all the samples. Tβ₄ mean concentration was 200 times higher in crevicular fluid (20 μmol/L, N = 9) than in whole saliva (0.1 μmol/L, N = 9). Crevicular fluid concentration of Tβ₄ (ca. 5% represented by its sulfoxide) and β₁₀ significantly correlated (r = 0.856; N = 9), and their ratio was about 5. A significant correlation was also observed between Tβ₄ concentrations in whole saliva and gingival crevicular fluid (r = 0.738; N = 9). Immunohistochemical analysis of the major salivary glands showed that immunoreactivity for Tβ₄ is restricted to ductal cells, with minor degree of focal positivity in some acinar cells. On the whole, results indicate that gingival sulcus is a main, although not the sole, source for oral Tβ₄ and Tβ₁₀.