Computer simulation of bottle-brush polymers with flexible backbone: good solvent versus theta solvent conditions

By molecular dynamics simulation of a coarse-grained bead-spring-type model for a cylindrical molecular brush with a backbone chain of N(b) effective monomers to which with grafting density σ side chains with N effective monomers are tethered, several characteristic length scales are studied for variable solvent quality. Side chain lengths are in the range 5 ≤ N ≤ 40, backbone chain lengths are in the range 50 ≤ N(b) ≤ 200, and we perform a comparison to results for the bond fluctuation model on the simple cubic lattice (for which much longer chains are accessible, N(b) ≤ 1027, and which corresponds to an athermal, very good, solvent). We obtain linear dimensions of the side chains and the backbone chain and discuss their N-dependence in terms of power laws and the associated effective exponents. We show that even at the theta point the side chains are considerably stretched, their linear dimension depending on the solvent quality only weakly. Effective persistence lengths are extracted both from the orientational correlations and from the backbone end-to-end distance; it is shown that different measures of the persistence length (which would all agree for Gaussian chains) are not mutually consistent with each other and depend distinctly both on N(b) and the solvent quality. A brief discussion of pertinent experiments is given.     

Towards the in vivo prediction of fragility fractures with Raman spectroscopy

Fragility fractures, those fractures which result from low level trauma, have a large and growing socio‐economic cost in countries with aging populations. Bone‐density‐based assessment techniques are vital for identifying populations that are at higher risk of fracture, but do not have high sensitivity when it comes to identifying individuals who will go on to have their first fragility fracture. We are developing Spatially Offset Raman Spectroscopy (SORS) as a tool for retrieving chemical information from bone non‐invasively in vivo. Unlike X‐ray‐based techniques SORS can retrieve chemical information from both the mineral and protein phases of the bone. This may enable better discrimination between those who will or will not go on to have a fragility fracture because both phases contribute to bone's mechanical properties. In this study we analyse excised bone with Raman spectroscopy and multivariate analysis, and then attempt to look for similar Raman signals in vivo using SORS. We show in the excised work that on average, bone fragments from the necks of fractured femora are more mineralised (by 5–10%) than (cadaveric) non‐fractured controls, but the mineralisation distributions of the two cohorts are largely overlapped. In our in vivo measurements, we observe similar, but as yet statistically underpowered, differences. After the SORS data (the first SORS measurements reported of healthy and diseased human cohorts), we identify methodological developments which will be used to improve the statistical significance of future experiments and may eventually lead to more sensitive prediction of fragility fractures. © 2015 The Authors. Journal of Raman Spectroscopy Published by John Wiley & Sons, Ltd.     

Antioxidant Serine-(NSAID) Hybrids with Anti-Inflammatory and Hypolipidemic Potency

A series of L-serine amides of antioxidant acids, such as Trolox, (E)-3-(3,5-di-tert-butyl-4-hydroxyphenyl)acrylic acid (phenolic derivative of cinnamic acid) and 3,5-di-tert-butyl-4-hydroxybenzoic acid (structurally similar to butylated hydroxytoluene), was synthesized. The hydroxy group of serine was esterified with two classical NSAIDs, ibuprofen and ketoprofen. The Trolox derivatives with ibuprofen (7) and ketoprofen (10) were the most potent inhibitors of lipid peroxidation (IC₅₀ 3.4 μΜ and 2.8 μΜ), several times more potent than the reference Trolox (IC₅₀ 25 μΜ). Most of the compounds decreased carrageenan-induced rat paw edema (37–67% at 150 μmol/kg). They were moderate inhibitors of soybean lipoxygenase, with the exception of ibuprofen derivative 8 (IC₅₀ 13 μΜ). The most active anti-inflammatory compounds exhibited a significant decrease in lipidemic indices in the plasma of Triton-induced hyperlipidemic rats, e.g., the most active compound 9 decreased triglycerides, total cholesterol and low-density lipoprotein cholesterol by 52%, 61% and 70%, respectively, at 150 μmol/kg (i.p.), similar to that of simvastatin, a well-known hypocholesterolemic drug. Since the designed compounds seem to exhibit multiple pharmacological actions, they may be of use for the development of agents against inflammatory and degenerative conditions.     

A Novel One- and Zero-Dimensional Model for Turbulent Jet Ignition

Flow, Turbulence and Combustion - Turbulent jet ignition (TJI) is a promising combustion technology for burning highly diluted air-fuel mixtures. Computationally efficient models to assess the...     

Silver polymeric nanocomposites as advanced antimicrobial agents: classification, synthetic paths, applications, and perspectives

Utilization of metallic nanoparticles in various biotechnological and medical applications represents one of the most extensively investigated areas of the current materials science. These advanced applications require the appropriate chemical functionalization of the nanoparticles with organic molecules or their incorporation in suitable polymer matrices. The intensified interest in polymer nanocomposites with silver nanoparticles is due to the high antimicrobial effect of nanosilver as well as the unique characteristics of polymers which include their excellent structural uniformity, multivalency, high degree of branching, miscellaneous morphologies and architectures, and highly variable chemical composition. In this review, we explore several aspects of antimicrobial polymer silver nanocomposites, giving special focus to the critical analysis of the reported synthetic routes including their advantages, drawbacks, possible improvements, and real applicability in antibacterial and antifungal therapy. A special attention is given to "green" synthetic routes exploiting the biopolymeric matrix and to the methods allowing preparing magnetically controllable antimicrobial polymers for targeting to an active place. The controversial mechanism of the action of silver against bacteria, fungi and yeasts as well as perspectives and new applications of silver polymeric nanocomposites is also briefly discussed.     

Single and Multiple Doping Effects on Charge Transport in Zigzag Silicene Nanoribbons

A non‐equilibrium Green’s function technique combined with density functional theory is used to study the spin‐dependent electronic band structure and transport properties of zigzag silicene nanoribbons (ZSiNRs) doped with aluminum (Al) or phosphorus (P) atoms. The presence of a single Al or P atom induces quasibound states in ZSiNRs that can be observed as new dips in the electron conductance. The Al atom acts as an acceptor whereas the P atom acts as a donor if it is placed at the center of the ribbon. This behavior is reversed if the dopant is placed on the edges. Accordingly, an acceptor–donor transition is observed in ZSiNRs upon changing the dopant’s position. Similar results are obtained if two silicon atoms are replaced by two impurities (Al or P atoms) but the conductance is generally modified due to the impurity–impurity interaction. If the doping breaks the twofold rotational symmetry about the central line, the transport becomes spin‐dependent.     

A macro-element to simulate 3D soil–structure interaction considering plasticity and uplift

In structural engineering, soil–structure interaction (SSI) is an important phenomenon that has to be taken into account. This paper presents a 3D non-linear interface element able to compute SSI based on the “macro-element” concept. The particularity of the macro-element lies in the fact that the movement of the foundation is entirely described by a system of generalised variables (forces and displacements) defined at the foundation centre. The non-linear behaviour of the soil and the uplift mechanism of the foundation are reproduced using the plasticity theory. The failure surface is defined using an adequate overturning mechanism. Coupling of the different mechanisms is straight forward following the theory of multi-mechanisms. The macro-element is able to simulate the 3D behaviour of a rigid shallow foundation of circular, rectangular or strip shape, submitted to cyclic loadings. It is implemented into FEDEASLab, a finite element MATLAB toolbox. Comparisons with experimental results under cyclic loadings show the performance of the approach.     

Influence of boundary conditions on the ordering of elastic dipoles

We consider elastic dipoles in several two-dimensional geometries. Using Cauchy integral techniques and the image method, the state of elastic equilibrium under different boundary conditions can be determined. The results are used to find the ground state of systems of anisotropic dipoles via the simulated annealing method. Only in the case of fixed boundaries the ordering depends on the boundary condition.     

The interface of buffer design and cyclic scheduling decisions in deterministic flow lines

In this paper, we address some issues on the interface of buffer design and cyclic scheduling decisions in a multi-product deterministic flow line. We demonstrate the importance of the above interface for the throughput performance of the flow line. In particular, we point out that the use of sequence-independent information, such as workload distribution and variability in processing times among stations, is not adequate to decide the optimal buffer configuration of the flow line. We formulate the buffer design problem for a fixed sequence of jobs as a general resource allocation problem, and suggest two effective heuristics for its solution. For the simultaneous buffer design and cyclic scheduling problem, we suggest an iterative scheme that builds on the effectiveness of the above heuristics. One of the side results of our extensive computational studies on this problem is that the general guidelines of buffer design in single-product flow lines with stochastic processing times are not directly transferable to the multiproduct deterministic flow line environment.