Two negative minima of the first normal stress difference in a cellulose‐based cholesteric liquid crystal: Helix uncoiling

The shear rate dependence of material functions such as shear viscosity (η) and the first normal stress difference (N₁) were given and interpreted earlier by Kiss and Porter. Their widely accepted work revealed the possibility of having a negative minimum of N₁ for polymeric liquid crystals. In this work, we disclose for the first time the evidence of two negative N₁ minima on a sheared cellulosic lyotropic system. The lower shear rate minimum is ascribed to the uncoiling of the cholesteric helix, as theoretically predicted earlier. Our findings contribute also to the understanding of the other minimum already reported in the literature and attributed to the nematic director tumbling mode. Moreover, the elastic change that the LC‐HPC sample undergoes during the helix unwinding of the cholesteric structure is also by means of oscillatory measurements. This study is a contribution for the understanding of the structure‐properties relationship linked with the complex rheological behavior of chiral nematic cellulose‐based systems and may help to improve their further processing. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 821–830     

Simple Characterization of Green-Synthesized Silver Nanoparticles by Capillary Electrophoresis

The development of methodologies for the characterization of silver nanoparticles (AgNPs) synthesized using natural products has received increasing attention, especially to monitoring its stability and size for further application. In this paper, a capillary electrophoretic (CE) method is presented for characterization of AgNPs synthesized using honey or glucose as reducing agents. A simple electrolyte solution composed of 20 mM sodium borate and 20 mM sodium dodecylsulfate (SDS) at pH 8.5 was used for separation of AgNPs within a short analysis time (<12 min). The obtained results were compared with the traditional characterization techniques, such as transmission electron microscopy (TEM) and dynamic light scattering (DLS), showing satisfactory correlation in terms of size distribution. In addition, valuable information about electrophoretic mobility and zeta potential values of AgNPs was obtained by applying the CE-UV/Vis method. Thus, the proposed methodology represents a straightforward tool for the fast and cost-effective characterization of AgNPs within a single analysis, employing minimal amounts of reagents and samples.     

Monitoring abiotic degradation of branched polyethylenes formulated with pro-oxidants through different mechanical tests

The mechanical properties of two linear low density and low density polyethylenes containing a pro-oxidant additive were monitored during accelerated aging (60 °C in a convection oven) and weather exposure. Tearing tests (trouser) were performed for the first time in polyethylenes subjected to oxo-degradation revealing a transition from an extensible to a non-extensible material, at exposure times when standard tensile tests were not able to detect any changes in the materials. The essential work of fracture (EWF) technique was also applied and the results were in agreement with those of trouser tests. The specific essential work of fracture first increased with exposure time until the sample experienced a transition to a less ductile state where EWF was no longer applicable. EWF and trouser tear tests were more sensitive detecting the onset of degradation probably because they employ notched specimens that impose more critical stress concentration conditions than conventional tensile tests.     

Structure and dynamics of biological liquid crystals

A review of thermodynamic and flow liquid crystal models is presented and applied to a wide range of biological liquid crystals (BLCs), including helicoidal plywoods, biopolymer solutions and in vivo liquid crystals. The key characteristics of liquid crystals (self-assembly, packing, defects, functionalities, processability) are discussed in relation to biological materials and the strong correspondence between different synthetic and biological materials is discussed. Viscoelastic models for nematic and chiral nematics are reviewed and discussed in terms of key parameters that facilitate understanding and quantitative information from experimental measurements. The range and consistency of the predictions demonstrates that the use of mesoscopic liquid crystal models is an efficient tool to develop the science and biomimetic applications of mesogenic biological materials.     

Structural Diversity from the Transannular Cyclizations of Natural Germacrone and Epoxy Derivatives: A Theoretical–Experimental Study

Treatment of germacrone ( 1 ) with different electrophiles, and of its epoxy derivatives germacrone‐4,5‐epoxide ( 2 ), germacrone‐1,10‐epoxide ( 3 ) and isogermacrone‐4,5‐epoxide ( 4 ) with Brönsted/Lewis acids and Ti^III, gives rise to a great structural diversity. Thus, by using a maximum of two steps, the production of more than 40 compounds corresponding to 14 skeletons is described. Computational calculations rationalizing the structural divergence produced are also described. Finally, since some of the compounds generated are bioactive natural sesquiterpenes, the mechanisms of formation of these substances will provide new insights in their biosynthesis.     

Gold‐Decorated Chiral Macroporous Films by the Self‐Assembly of Functionalised Block Copolymers

We describe a new and very versatile method to place chosen chemical functionalities at the edge of the pores of macroporous materials. The method is based on the synthesis and self‐assembly of inorganic block copolymers (BCPs) having chiral rigid segments bearing controllable quantities of randomly distributed functional groups. The synthesis of a series of optically active block copolyphosphazenes (PP) with the general formula [N?P(R‐O₂C₂₀H₁₂)_0.9(FG)_0.2]_n‐b‐[N?PMePh]_m (FG=‐OC₅H₄N ( 6 ), ‐NC₄H₈S ( 7 ), and ‐NC₄H₈O ( 8 )), was accomplished by the sequential living cationic polycondensation of N‐silylphosphoranimines, using the mono‐end‐capped initiator [Ph₃P?N?PCl₃][Cl] ( 3 ). The self‐assembly of the phosphazene BCPs 6 – 8 led to chiral porous films. The functionality present on those polymers affected their self‐assembly behaviour resulting in the formation of pores of different diameters (D_n=111 ( 6 ), 53 ( 7 ) and 77 nm ( 8 )). The specific functionalisation of the pores was proven by decorating the films with gold nanoparticles (AuNPs). Thus, the BCPs 6 and 7 , having pyridine and thiomorpholine groups, respectively, were treated with HAuCl₄, followed by reduction with NaBH₄, yielding a new type of block copolyphosphazenes, which self‐assembled into chiral porous films specifically decorated with AuNPs at the edge of the pores.     

Consequences of weak Allee effect on prey in the May–Holling–Tanner predator–prey model

In this work, a modified Holling–Tanner predator–prey model is analyzed, considering important aspects describing the interaction such as the predator growth function is of a logistic type; a weak Allee effect acting in the prey growth function, and the functional response is of hyperbolic type. Making a change of variables and time rescaling, we obtain a polynomial differential equations system topologically equivalent to the original one in which the non‐hyperbolic equilibrium point (0,0) is an attractor for all parameter values. An important consequence of this property is the existence of a separatrix curve dividing the behavior of trajectories in the phase plane, and the system exhibits the bistability phenomenon, because the trajectories can have different ω ? limit sets; as example, the origin (0,0) or a stable limit cycle surrounding an unstable positive equilibrium point. We show that, under certain parameter conditions, a positive equilibrium may undergo saddle‐node, Hopf, and Bogdanov–Takens bifurcations; the existence of a homoclinic curve on the phase plane is also proved, which breaks in an unstable limit cycle. Some simulations to reinforce our results are also shown. Copyright © 2015 John Wiley & Sons, Ltd.     

Regiospecific synthesis of 1-acetamide-5-methoxy-2-oxindoles in two steps: (Ugi-SN2)/xanthate mediated free radical cyclization

A series of twelve novel 1-acetamide-5-methoxy-2-oxindoles were prepared in moderate to good yields (30–88%) by an Ugi-S_N2 one pot process with a xanthate mediated free radical cyclization. Additionally, Density Functional Theory (DFT) based calculations were performed at UB3LYP/6-311G(d) level in order to rationalize the energy profile of the xanthate mediated free radical cyclization because the benzo-fused γ-lactams (ortho products) were obtained as sole regioisomers over the spiro β-lactams (ipso products).