The first synthesis of N-acetylneuraminic acid 1,7-lactone

N-Acetylneuraminic acid is transformed into its until now unavailable and rather unwieldy 1,7-lactone, via the manageable 2-benzyloxycarbonyl N-acetylneuraminic acid 1,7-lactone which generates the free lactone in quantitative yield by hydrogenolysis.     

The electron photodetachment spectrum of c-C4F8-: a test case for the computation of Franck-Condon factors of highly flexible molecules

The long (approximately 20 000 cm(-1)) vibrational progression observed in the electron photodetachment spectrum of c-C(4)F(8)(-) anion is analyzed in terms of the Franck-Condon factors between the ground electronic states of the anionic and neutral species. The observed spectrum is correctly reproduced and its vibronic structure is assigned in detail. The very simple structure of the spectrum, consisting of a sequence of evenly spaced peaks, at 355 cm(-1) each other, is assigned to a series of overlapping progressions associated with vibrational excitations of two totally symmetric modes rather than to a single mode progression, as originally proposed. The underlying continuum observed in the experimental spectrum is traced back to the excitations of a low frequency ring-puckering vibration, which, in the neutral species, exhibits a double minimum potential energy profile.     

On the convergence of the Fitness-Complexity algorithm

We investigate the convergence properties of an algorithm which has been recently proposed to measure the competitiveness of countries and the quality of their exported products. These quantities are called respectively Fitness F and Complexity Q. The algorithm was originally based on the adjacency matrix M of the bipartite network connecting countries with the products they export, but can be applied to any bipartite network. The structure of the adjacency matrix turns to be essential to determine which countries and products converge to non zero values of F and Q. Also the speed of convergence to zero depends on the matrix structure. A major role is played by the shape of the ordered matrix and, in particular, only those matrices whose diagonal does not cross the empty part are guaranteed to have non zero values as outputs when the algorithm reaches the fixed point. We prove this result analytically for simplified structures of the matrix, and numerically for real cases. Finally, we propose some practical indications to take into account our results when the algorithm is applied.     

Structural and rheological investigation of Fd3m inverse micellar cubic phases

In the present study we demonstrate that a bulk inverse micellar cubic phase of Fd3m structure can be obtained by adding a hydrophobic component, such as the food-grade limonene, to the binary system monolinolein/water in a well-defined composition. The Fd3m structure studied in this work had a very slow kinetics of formation, as a consequence of partitioning of water into two types of micelle populations with different sizes. The Fd3m structure formed at a ratio of limonene oil to total lipids of alpha = 0.4 is stable in the bulk up to a maximum hydration of 12.68 wt % water, beyond which it starts to coexist with dispersed water. At full hydration, by combining small-angle X-ray scattering and available topological models, the inverse micellar cubic phase of Fd3m structure was shown to be formed by 16 small micelles and 8 larger micelles per cubic lattice cell (Q227 group), with radii of the micellar polar cores ranging between 1 and 3 nm and 149-168 monolinolein molecules per micelle depending on the water content. The temperature dependence of the structural and rheological properties of the Fd3m mesophase was investigated using SAXS, rheology, and turbidimetry. It appeared that the Fd3m phase underwent crystallization below 18 degrees C and began melting in an inverse microemulsion (L2 phase) coexisting with water above 28.5 degrees C with complete melting obtained at 40-45 degrees C, as evidenced by SAXS and rheology. Macroscopic phase separation between the L2 phase and excess water was observed with time at higher temperatures. The investigation of the viscoelastic properties of the Fd3m inverse discrete micellar cubic phase revealed a rheological signature similar to that of the bicontinuous cubic phases Pn3m and Ia3d observed in homologous binary systems. However, the Fd3m phase presented a complex set of slower relaxation mechanisms leading to a shift by 1 order of magnitude of the dominant relaxation times and whole relaxation spectrum, as compared to those of inverse bicontinuous cubic phases. These findings have been tentatively explained by (i) the multiple relaxation of micelles upon deformation, (ii) the small hydration level of the Fd3m phase, and (iii) the low temperature at which this phase can be observed.     

Berry phase approach to longitudinal dipole moments of infinite chains in electronic-structure methods with local basis sets

The authors provide a reformulation of the modern theory of polarization for one-dimensional stereoregular polymers, at the level of the single determinant Hartree-Fock and Kohn-Sham methods within a basis set of local orbitals. By starting with localization of one-electron orbitals, their approach naturally arrives to the Berry phases of Bloch orbitals. Then they describe a novel numerical algorithm for evaluation of longitudinal dipole moments, computationally more convenient than those presently implemented within the local basis periodic codes. This method is based on the straightforward evaluation of the usual direct space dipole matrix elements between local orbitals, as well as overlap matrices between wave functions at two neighboring k points of the reciprocal space mesh. The practical behavior of the algorithm and its convergence properties with respect to the k-point mesh density are illustrated in benchmark calculations for water chains and fluorinated trans-polyacetylene.     

Secondary metabolism of olive secoiridoids. New microcomponents detected in drupes by electrospray ionization and high-resolution tandem mass spectrometry

Olive drupe tissues have been selected as a possible source of information about the secondary metabolism of oleaceae secoiridoids. The structures of a number of new microcomponents, detected and isolated by a combined high-performance liquid chromatography (HPLC)-fraction collector/ultraviolet electrospray ionization mass spectrometry (UV/ESI-MS) apparatus, can be inferred from the data obtained by high-resolution tandem mass spectrometry in a QqTOF instrument. Some of them (1, 2, 3 and 4) are closely correlated to oleuropein. Others, such as neo-nuzhenide (5) and 2'-hydroxyoleuropein (6), typical of other oleaceae families, have never been found in olive tissues.     

Conceptual polymorphism of entropy into the history: extensions of the second law of thermodynamics towards statistical physics and chemistry during nineteenth–twentieth centuries

After the birth of thermodynamics’ second principle—outlined in Carnot's Réflexions sur la puissance motrice du feu (1824)—several studies provided new arguments in the field. Mainly, they concerned the thermodynamics’ first principle—including energy conceptualisation—, the analytical aspects of the heat propagation, the statistical aspects of the mechanical theory of heat. In other words, the second half of nineteenth century was marked by an intense interdisciplinary research activity between physics and chemistry: new disciplines applied to the heat developed in the form of analytical, mechanical and statistical theories. Inside all these theories, entropy—the brand-new function that Clausius coined in his Mechanical theory of heat—started to play a central epistemic role. In the present paper, we analyse some steps of the historical process of conceptualisation of such function from 1850 to 1902. Particularly, we retrace the historical–foundational path that—starting from Clausius’ Second Law—lead Boltzmann and Gibbs to their distinguished formulations of statistical entropy. As usual, our research has been unrolled through the analyses of primary sources and by leaning on critical readings of the secondary literature. As for the methodological approach, text analysis of historical documents constituted our privileged modus operandi. This paper is the expression of a collaborative historical research program focused on the thermodynamic foundations of physics–chemistry relationship; early results have already been published by the same authors upon the concepts of reversibility––and––thermal equilibrium.

     

Anomalous phase sequences in lyotropic liquid crystals

We present a coarse-grained model in order to describe the unusual sequence of mesophases observed in aqueous solutions of nonionic lipids, such as monoolein. The lipid molecules are modeled as a rigid head and a flexible Gaussian tail, and water is treated explicitly. A key component of the model is thermally reversible hydrogen bonding between the lipid head and water resulting in changes in both head volume and the interactions of the hydrated head with its surroundings. Phase diagrams obtained from unit-cell self-consistent field simulations capture the qualitative thermotropic and lyotropic phase behavior of the monoolein-water system. The unusual phase sequences result from a competition between hydrogen bond formation, changes in head volume and interactions, lipid tail entropy, and the hydrophobic effect.     

Influence of the β‐Sheet Content on the Mechanical Properties of Aggregates during Amyloid Fibrillization

Amyloid fibrils associated with neurodegenerative diseases, such as Parkinson’s and Alzheimer’s, consist of insoluble aggregates of α‐synuclein and Aβ‐42 proteins with a high β‐sheet content. The aggregation of both proteins occurs by misfolding of the monomers and proceeds through the formation of intermediate oligomeric and protofibrillar species to give the final fibrillar cross‐β‐sheet structure. The morphological and mechanical properties of oligomers, protofibrils, and fibrils formed during the fibrillization process were investigated by thioflavin T fluorescence and circular dichroism in combination with AFM peak force quantitative nanomechanical technique. The results reveal an increase in the Young’s modulus during the transformation from oligomers to mature fibrils, thus inferring that the difference in their mechanical properties is due to an internal structural change from a random coil to a structure with increased β‐sheet content.