Reactive dissolution of cellulose and pulp through acylation in pyridine

The direct acylation of cellulose and different pulps with various acid chlorides was systematically screened. The syntheses were started in a heterogeneous solid–liquid reaction medium in hot pyridine with aliphatic and aromatic acid chlorides. After a few hours, depending on the reagent used, a homogenous solution was obtained. The obtained cellulose esters usually show a high degree of substitution (DS) and polymerization and are soluble in organic solvents. Esterification of softwood dissolving pulp, hardwood kraft pulp and hardwood kraft pulp-hemicellulose poor were also studied. The results show that almost identical DS were obtained for pulp derivatives compared to esters of microcrystalline cellulose. Thermogravimetric analysis and differential scanning calorimetry of the synthesized materials showed an improved thermal stability and various discrete thermal transitions compared to the original cellulose. The scanning electron microscopy images of derivatives showed a relatively flat and smooth surface with an absence of fibrous structure. The reactive dissolution of cellulose or pulp in pyridine is a straightforward and easy route to obtain long-chain aliphatic and aromatic cellulose esters.     

A recovery‐based error estimator for finite volume methods of interface problems: Conforming linear elements

In this article, we present a recovery‐based a posteriori error estimator for finite volume methods which use the conforming linear trial functions to approximate elliptic interface problems. The reliability and efficiency bounds for the error estimator are established by recovering the flux from a weighted L² projection to H(div) conforming finite element spaces. Numerical experiments are given to support the conclusions. © 2012 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 2013     

Limitations of superoscillation filters in microscopy applications

The idea of superresolving pupil filters comes from the concept of superoscillations that may occur in regions of a band-limited signal with small amplitude having oscillations faster than the fastest Fourier component of the signal. In optical microscopy, superresolution can be achieved by appropriate design of pupil functions where the angular aperture determines the ultimate focal spot smaller than the Abbe diffraction limit outside the evanescent field region. The angular aperture cannot be increased indefinitely and the huge sidelobes cannot be avoided that are present in superresolving filters. The limitations of using such kind of filters in microscopy applications are discussed through computational examples.     

Matrix Gla protein inhibits ectopic calcification by a direct interaction with hydroxyapatite crystals

Mice lacking the gene encoding matrix gla protein (MGP) exhibit massive mineral deposition in blood vessels and die soon after birth. We hypothesize that MGP prevents arterial calcification by adsorbing to growing hydroxyapatite (HA) crystals. To test this, we have used a combined experimental-computational approach. We synthesized peptides covering the entire sequence of human MGP, which contains three sites of serine phosphorylation and five sites of γ-carboxylation, and studied their effects on HA crystal growth using a constant-composition autotitration assay. In parallel studies, the interactions of these sequences with the {100} and {001} faces of HA were analyzed using atomistic molecular dynamics (MD) simulations. YGlapS (amino acids 1-14 of human MGP) and SK-Gla (MGP43-56) adsorbed rapidly to the {100} and {001} faces and strongly inhibited HA growth (IC(50) = 2.96 μg/mL and 4.96 μg/mL, respectively). QR-Gla (MGP29-42) adsorbed more slowly and was a moderate growth inhibitor, while the remaining three (nonpost-translationally modified) peptides had little or no effect in either analysis. Substitution of gla with glutamic acid reduced the adsorption and inhibition activities of SK-Gla and (to a lesser extent) QR-Gla but not YGlapS; substitution of phosphoserine with serine reduced the inhibitory potency of YGlapS. These studies suggest that MGP prevents arterial calcification by a direct interaction with HA crystals that involves both phosphate groups and gla residues of the protein. The strong correlation between simulated adsorption and measured growth inhibition indicates that MD provides a powerful tool to predict the effects of proteins and peptides on crystal formation.     

The application of solid sorbents for the purification of aluminum contaminated chemicals used as modifiers in electrothermal atomic absorption spectrometry

Various microcolumns with solid sorbents (ion exchange resins, functionalised cellulose sorbents, chelating resins) have been tested with respect to their ability for the purification of aluminum contaminated chemicals used as modifiers in electrothermal atomic absorption spectrometry. The purification of NaNO₃, Mg(NO₃)₂, K₂SO₄ and (NH₄)₂HPO₄ has been the most effective with an almost 100% efficiency, when Spheron-Oxine was used as chelating resin. The sorption of aluminum from KOH solution has been found to be very high (around 90%) for all investigated sorbents. However, the best results have been obtained with anion-exchange resins. It has been difficult to purify concentrated mineral acids (HCl, H₂SO₄). A retention of aluminum above 80% has been achieved only when Cellex P, Chelex 100 or Amberlite XAD-2 have been used.     

Constraints on sparticle spectrum in different supersymmetry breaking models

We derive sum rules for the sparticle masses in different models of supersymmetry breaking. This includes the gravity-mediated models (SUGRA models) as well as models in which supersymmetry breaking terms are induced by super-Weyl anomaly (AMSB models). These sum rules can help in distinguishing between these models. In particular, we obtain an upper bound on the mass of the lightest neutralino as a function of the gluino mass in SUGRA and AMSB models.     

From calls to communities: a model for time-varying social networks

Social interactions vary in time and appear to be driven by intrinsic mechanisms thatshape the emergent structure of social networks. Large-scale empirical observations ofsocial interaction structure have become possible only recently, and modelling theirdynamics is an actual challenge. Here we propose a temporal network model which builds onthe framework of activity-driven time-varying networks with memory. Themodel integrates key mechanisms that drive the formation of social ties – socialreinforcement, focal closure and cyclicclosure, which have been shown to give rise to community structure andsmall-world connectedness in social networks. We compare the proposed model with areal-world time-varying network of mobile phone communication, and show that they shareseveral characteristics from heterogeneous degrees and weights to rich communitystructure. Further, the strong and weak ties that emerge from the model follow similarweight-topology correlations as real-world social networks, including the role of weakties.     

Computational methods for analysis of an unsaturated carbocycle: heptafulvene

With respect to geometric optimizations, harmonic vibrational frequencies and single point conformational energies, various computational methods [HF, MP2, CCSD(T), BD(T), CASSCF, CASPT2, and DFT] were evaluated for their suitability to describe the heptafulvene system. We found that a significant number of basis sets lead to wrong predictions of folded minima, when ab initio methods including dynamic electron correlation are used. Possible explanations for these inconsistencies, such as wave function instabilities, near linear dependences of the basis sets and inadequate inclusion of polarization functions in the basis set, are discussed. Such concerns are likewise important for other classes of π-conjugated compounds, such that the results are expected to be of interest not only for heptafulvenes.