Spreading measures of information-extremizer distributions: applications to atomic electron densities in position and momentum spaces

The problem of finding the information-extremizer distribution with a set of given constraints (partial information) has a relevant role from both physical and chemical points of view, specially when working within a density functional theory framework. Beyond the variance, there exist different measures of information susceptible of being extremized, such as the Fisher information and the Shannon and Tsallis entropies. Each one possesses its own properties which make their use more or less convenient according to the systems and/or the process we are dealing with. In this work, we analyze the main information measures of the electron densities of neutral atoms throughout the periodic table, in the two conjugated position and momentum spaces. It is shown how these measures display shell-filling patterns, within a level which depends on the information measure and the space considered. Additionally, the values of all these measures for the solution of various atomic information extremization problems (MaxEnt, MaxTent, MinInf), using radial expectation values as constraints, are analytically obtained, numerically evaluated and also interpreted and discussed in terms of physical characteristics of the atomic systems, such as periodicity and shell structure.     

New low-energy measurement of the 18F(p,α)15O reaction

The ¹⁸F, produced during nova explosions, is the main responsible for the 511 keV γ-ray emitted during the outburst that could be detected with satellite missions or future γ-ray telescopes. In spite of many experimental efforts, the amount of ¹⁸F synthesized still suffers from large uncertainties concerning mainly the ¹⁸F(p,α)¹⁵O reaction. We report here on a new direct measurement of the ¹⁸F(p,α)¹⁵O cross section recently carried out at the RIB facility at Louvain-la-Neuve. Cross section data down to a center-of-mass energy of 400 keV have been obtained using an isobarically pure ¹⁸F beam (averaged intensity of the order of 10⁶ pps) and a thin polyethylene target. The reaction products were detected using the multi-strip detector array LEDA. The cross section data are analysed in the framework of the R-matrix model. Our main aim is to determine the interference sign between three 3/2⁺ resonances above threshold that can significantly affect the extrapolation of the ¹⁸F(p,α)¹⁵O cross section to the energies relevant for novae, and thus, the modeling of nova explosions.     

Synthesis,Biological Evaluation,WAC and NMR Studies of S‐Galactosides and Non‐Carbohydrate Ligands of Cholera Toxin Based on Polyhydroxyalkylfuroate Moieties

The synthesis of several non‐carbohydrate ligands of cholera toxin based on polyhydroxyalkylfuroate moieties is reported. Some of them have been linked to D ‐galactose through a stable and well‐tolerated S‐glycosidic bond. They represent a novel type of non‐hydrolyzable bidentate ligand featuring galactose and polyhydroxyalkylfuroic esters as pharmacophoric residues, thus mimicking the GM1 ganglioside. The affinity of the new compounds towards cholera toxin was measured by weak affinity chromatography (WAC). The interaction of the best candidates with this toxin was also studied by saturation transfer difference NMR experiments, which allowed identification of the binding epitopes of the ligands interacting with the protein. Interestingly, the highest affinity was shown by non‐carbohydrate mimics based on a polyhydroxyalkylfuroic ester structure.     

Chemoenzymatic Synthesis of Fluorinated Cellodextrins Identifies a New Allomorph for Cellulose-Like Materials**

Understanding the fine details of the self-assembly of building blocks into complex hierarchical structures represents a major challenge en route to the design and preparation of soft-matter materials with specific properties. Enzymatically synthesised cellodextrins are known to have limited water solubility beyond DP9, a point at which they self-assemble into particles resembling the antiparallel cellulose II crystalline packing. We have prepared and characterised a series of site-selectively fluorinated cellodextrins with different degrees of fluorination and substitution patterns by chemoenzymatic synthesis. Bearing in mind the potential disruption of the hydrogen-bond network of cellulose II, we have prepared and characterised a multiply 6-fluorinated cellodextrin. In addition, a series of single site-selectively fluorinated cellodextrins was synthesised to assess the structural impact upon the addition of one fluorine atom per chain. The structural characterisation of these materials at different length scales, combining advanced NMR spectroscopy and microscopy methods, showed that a 6-fluorinated donor substrate yielded multiply 6-fluorinated cellodextrin chains that assembled into particles presenting morphological and crystallinity features, and intermolecular interactions, that are unprecedented for cellulose-like materials.     

A numerical integrator for a model with a discontinuous sink term: the dynamics of the sexual phase of monogonont rotifera

We present an explicit numerical method especially adapted to approximate the solution of a nonlinear model with a discontinuous sink term: the dynamics of the sexual phase of monogonont rotifera. We show the effectiveness of this numerical technique in the simulation of the dynamics of the solutions. In particular, we show that this method provides a good approximation to the equilibrium solution of the problem. On the other hand, the numerical simulation presented validates the asymptotic behaviour of the numerical solution with regard to the theoretical one.     

Resveratrol augments ER stress and the cytotoxic effects of glycolytic inhibition in neuroblastoma by downregulating Akt in a mechanism independent of SIRT1

Cancer cells typically display increased rates of aerobic glycolysis that are correlated with tumor aggressiveness and a poor prognosis. Targeting the glycolytic pathway has emerged as an attractive therapeutic route mainly because it should spare normal cells. Here, we evaluate the effects of combining the inhibition of glycolysis with application of the polyphenolic compound resveratrol (RSV) in neuroblastoma (NB) cancer cell lines. Inhibiting glycolysis with 2-deoxy-D-glucose (2-DG) significantly reduced NB cell viability and was associated with increased endoplasmic reticulum (ER) stress and Akt activity. Administration of 2-DG increased the expression of the ER molecular chaperones GRP78 and GRP94, the prodeath protein C/EBP homology protein (CHOP) and the phosphorylation of Akt at S473, T450 and T308. Combined treatment with both RSV and 2-DG reduced GRP78, GRP94 and Akt phosphorylation but increased CHOP and NB cell death when compared with the administration of 2-DG alone. The selective inhibition of Akt activity also decreased 2-DG-induced GRP78 and GRP94 expression and increased CHOP expression, suggesting that Akt can modulate ER stress. Protein phosphatase 1α (PP1α) was activated by RSV, as indicated by a reduction in PP1α phosphorylation at T320. Pretreatment of cells with tautomycin, a selective PP1α inhibitor, prevented the RSV-mediated decrease in Akt phosphorylation, suggesting that RSV enhances 2-DG-induced cell death by activating PP1 and downregulating Akt. The RSV-mediated inhibition of Akt in the presence of 2-DG was not prevented by the selective inhibition of SIRT1, a known target of RSV, indicating that the effects of RSV on this pathway are independent of SIRT1. We propose that RSV inhibits Akt activity by increasing PP1α activity, thereby potentiating 2-DG-induced ER stress and NB cell death.     

Intramolecular charge-transfer dynamics in covalently linked perylene-dimethylaniline and cyanoperylene-dimethylaniline

The excited-state dynamics of covalently linked electron donor-acceptor systems consisting of N, N-dimethylaniline (DMA) as electron donor and either perylene (Pe) or cyanoperylene (CNPe) as acceptor has been investigated in a large variety of solvents, including a room-temperature ionic liquid, by using femtosecond time-resolved fluorescence and absorption spectroscopy. The negligibly small solvent dependence of the absorption spectrum of both compounds and the strong solvatochromism of the fluorescence are interpreted by a model where optical excitation results in the population of a locally excited state (LES) and emission takes place from a charge-separated state (CSS). This interpretation is supported by the fluorescence up-conversion and the transient absorption measurements that reveal substantial spectral dynamics in polar solvents only, occurring on time scales going from a few hundreds of femtoseconds in acetonitrile to several tens of picoseconds in the ionic liquid. The early transient absorption spectra are similar to those found in nonpolar solvents and are ascribed to the LES absorption. The late spectra due to CSS absorption show bands that are red-shifted relative to those of the radical anion of the acceptor moiety by an amount that depends on solvent polarity, pointing to partial charge separation. Global analysis of the time-resolved data indicates that the charge separation dynamics in PeDMA is essentially solvent controlled, whereas that in CNPeDMA is faster than diffusive solvation, this difference being accounted for by a larger driving force for charge separation in the latter. On the other hand, the CSS lifetime of PeDMA is of the order of a few nanoseconds independently of the solvent, whereas that of CNPeDMA decreases with increasing solvent polarity from a few nanoseconds to a few hundreds of picoseconds. Comparison of these results with previously published data on the fluorescence quenching of Pe and CNPe in pure DMA shows that the charge separation and the ensuing charge recombination occur on similar time scales independently of whether these processes are intra- or intermolecular.     

Fingerprinting of human bile during liver transplantation by capillary electrophoresis

Increasing rates of success in liver transplantation have increased the number of cases considered. However, liver post-transplant graft dysfunction of liver transplants (TXs) is not fully understood and by applying holistic approaches we can investigate metabolic change deriving from confounding factors such as liver fat content, ischaemia time, donor age, recipient's health, etc. Twenty-six hepatic bile samples taken from liver donors and recipients were retrieved from a total of six TXs, from these one recipient underwent post-graft dysfunction. CE was employed to fingerprint bile collected at 10 min increments in the donors and in the recipients. The electropherograms of these samples were aligned and normalised using correlation optimised warping algorithms and modelled with multivariate techniques. The resulting metabolic signatures were compared; in general donors and recipients showed distinct fingerprints and clustered separately. When a partial least square discriminant analysis (PLS-DA) model was constructed between donor and recipient's samples, a recipient of a 32 year old liver with normal steatosis, and shortest cold ischaemia time showed as the observation nearest to its donor observation, denoting minimal metabolic change. This study proposes CE fingerprinting of human bile as a promising technique to help unravel the complex metabolic pathways involved during transplantation.     

New perspective of diabetes response to an antioxidant treatment through metabolic fingerprinting of urine by capillary electrophoresis

Benefits of capillary electrophoresis to provide a comprehensive snapshot of multiple metabolites in biological samples have been exploited. Afterwards, multivariate statistical methods can be employed in order to mine additional information from the data. Urine fingerprints of control and diabetic rats have shown the clear effects of an antioxidant treatment on diabetic animals, which were not seen in controls, in a rapid, simple and cost-effective way without identifying a single marker. The procedure involves the measurement of samples with a relatively inexpensive tool such as CE-UV, without any previous treatment other than filtration and the application of chemometric tools [PCA (principal components analysis) and PLS-DA (partial least squares discriminant analysis)]. Data pre-treatment of electrophoretic profiles (alignment, normalization and baseline correction) has shown to be key for further chemometric treatment. Once developed, the methodology can easily be applied for a rapid in vivo screening of extracts with potential in vitro activity. Classification was supported by that produced after PCA and PLS-DA of target variables obtained with selectively designed, time and reagent consuming methods.     

Transverse Orbital Stability of Periodic Traveling Waves for Nonlinear Klein–Gordon Equations

In this paper, we establish the orbital stability of a class of spatially periodic wave train solutions to multidimensional nonlinear Klein–Gordon equations with periodic potential. We show that the orbit generated by the one‐dimensional wave train is stable under the flow of the multidimensional equation under perturbations which are, on one hand, coperiodic with respect to the translation or Galilean variable of propagation, and, on the other hand, periodic (but not necessarily coperiodic) with respect to the transverse directions. That is, we show their transverse orbital stability. The class of periodic wave trains under consideration is the family of subluminal rotational waves, which are periodic in the momentum but unbounded in their position.