Dielectric relaxation of water molecules in different lyotropic structures of nonylphenoxypoly(ethylenoxy)ethanol (Ark. 9)

Abstract

Dielectric relaxation of water molecules in the lamellar, L_α, cubic and hexagonal, H_α, lyotropic structures of nonylphenoxy-poly(ethylenoxy)ethanol (Ark. 9) has been studied by dielectric time domain spectroscopy in the frequency range between 10 MHz and 10 GHz. The values of the relaxation times, obtained at room temperature, are the following: 41 ps for the L_α phase, 29 ps for the cubic phase and 22 ps for the H_α phase. As is seen, the relaxation time of bound water is distinctly higher than that of pure water, and it depends strongly on the phase structure. The relaxation times measured for the liquid-crystalline phases as well as for pure Ark. 9 obey the Arrhenius law, and the energy barriers obtained have the following values: (20 ± 2) kJ/mol for all the liquid-crystalline phases, and (30 ± 3) kJ/mol for pure Ark. 9. The former is in good agreement with the value found for bound water in lipid systems whereas the latter is characteristic of the isotropic phase of thermotropic liquid crystals.     

Ultra‐high pressure LC for astaxanthin determination in shrimp by‐products and active food packaging

Nowadays, there is increasing interest in natural antioxidants from food by‐products. Astaxanthin is a potent antioxidant and one of the major carotenoids in crustaceans and salmonids. An ultra‐high pressure liquid chromatographic method was developed and validated for the determination of astaxanthin in shrimp by‐products, and its migration from new packaging materials to food simulants was also studied. The method uses an UPLC® BEH guard‐column (2.1 × 5 mm, 1.7 µm particle size) and an UPLC® BEH analytical column (2.1 × 50 mm, 1.7 µm particle size). Chromatographic separation was achieved using a programmed gradient mobile phase consisting of (A) acetonitrile–methanol (containing 0.05 m ammonium acetate)–dichloromethane (75:20:5, v/v/v) and (B) ultrapure water. This method was evaluated with respect to validation parameters such as linearity, precision, limit of detection, limit of quantification and recovery. Low‐density polyethylene films were prepared with different amounts of the lipid fraction of fermented shrimp waste by extrusion, and migration was evaluated into food simulants (isooctane and ethanol 95%, v/v). Migration was not detected under the tested conditions. Copyright © 2012 John Wiley & Sons, Ltd.     

Lagrangian submanifolds in k-symplectic settings

In this paper we extend the well-know normal form theorem for Lagrangian submanifolds proved by Weinstein in symplectic geometry to the setting of k-symplectic manifolds.     

Synthesis of the four enantiomers of diethyl 1,2-di(N-Boc-amino)propylphosphonates

A simple and efficient synthetic strategy to all four enantiomerically pure diethyl 1,2-di(N-Boc-amino)propylphosphonates has been elaborated starting from the corresponding N-[(R)-(1-phenylethyl)]aziridine-(2S)- and N-[(S)-(1-phenylethyl)]aziridine-(2R)-carboxaldehydes, employing a one-pot three-components Kabachnik-Fields reaction followed by the hydrogenolytic removal of the chiral auxiliary and aziridine ring opening with simultaneous protection of the amino groups as the N-Boc derivatives.     

Fracture Characterization of Steels by Means of the Small Punch Test

A hot rolled API X-70 steel plate and its heat-affected zone (the region with the maximum hardness and lowest toughness of the welded joint made using this steel) were employed to obtain the material’s room temperature elasto-plastic fracture toughness, J_Ic, by means of small punch tests (SPTs) using both conventional un-notched samples and longitudinally-notched SPT specimens. In the latter case, the notches were manufactured by micromachining different notch depth-to-thickness ratios (a/t?=?0.3 and 0.4). The representative toughness parameter used with the conventional SPT tests was the maximum strain measured directly in the failed region, while in the case of the notched samples, the consumed energy until the initiation of a crack from the tip of the notch was considered the most useful parameter of choice. The onset of crack initiation was determined directly from the load-displacement plot of each test with the aid of scanning electron microscope observations performed on different samples over which interrupted tests had been conducted. These tests were interrupted at different percentages of the maximum registered load. A simple correlation between the energy consumed until the initiation of crack growth in the notched SPT sample and the critical J value obtained using standard tests (J-R curves) was determined, defining an easy and promising way to derive fracture toughness from miniature SPT tests.     

Covalent Cross-Linking of 2H-MoS2 Nanosheets

The combination of 2D materials opens a wide range of possibilities to create new-generation structures with multiple applications. Covalently cross-linked approaches are a ground-breaking strategy for the formation of homo or heterostructures made by design. However, the covalent assembly of transition metal dichalcogenides flakes is relatively underexplored. Here, a simple covalent cross-linking method to build 2H-MoS₂–MoS₂ homostructures is described, using commercially available bismaleimides. These assemblies are mainly connected vertically, basal plane to basal plane, creating specific molecular sized spaces between MoS₂ sheets. Therefore, this straightforward approach gives access to the controlled connection of sulfide-based 2D materials.     

Functionalization of cellulose nanocrystal powder by non-thermal atmospheric-pressure plasmas

Cellulose - Despite promising characteristics such as the biodegradability and the environmentally benign nature of cellulose nanocrystal (CNC) based composites, their poor dispersion and...     

The Coordinate Reaction Model: An Obstacle to Interpreting the Emergence of Chemical Complexity

The way chemical transformations are described by models based on microscopic reversibility does not take into account the irreversibility of natural processes, and therefore, in complex chemical networks working in open systems, misunderstandings may arise about the origin and causes of the stability of non-equilibrium stationary states, and general constraints on evolution in systems that are far from equilibrium. In order to be correctly simulated and understood, the chemical behavior of complex systems requires time-dependent models, otherwise the irreversibility of natural phenomena is overlooked. Micro reversible models based on the reaction-coordinate model are time invariant and are therefore unable to explain the evolution of open dissipative systems. The important points necessary for improving the modeling and simulations of complex chemical systems are: a) understanding the physical potential related to the entropy production rate, which is in general an inexact differential of a state function, and b) the interpretation and application of the so-called general evolution criterion (GEC), which is the general thermodynamic constraint for the evolution of dissipative chemical systems.