Analytic description of enhanced backscattering and negative polarization from a cloud of dipoles

We develop a second-order model of the light scattered by a cloud of randomly positioned dipoles and consider the interference of reciprocal rays that lead to enhanced backscatter and negative polarization. For large pathlength separations, we derive analytic expressions for the individual polarization intensities.     

Time-dependent electrical properties of liquid crystal cells: unravelling the origin of ion generation

An understanding of possible sources of ion generation in liquid crystal materials is of utmost importance to ensure uncompromised performance of modern liquid crystal devices. In this paper, time-dependent electrical properties of filled liquid crystal cells are used to reveal important information about often overlooked source of ion generation in liquid crystals. This source of ions originates from the ionic contamination of substrates of the liquid crystal cell. Ionic contaminants can be inherently present in the alignment layers or can be induced by external factors such as mechanical rubbing or irradiation with light. The model of this ion generation process is presented and tested using existing experimental data.     

Kinetics and mechanism of alkane hydroperoxidation with tert-butyl hydroperoxide catalysed by a vanadate anion

tert-Butyl hydroperoxide oxidizes alkanes in acetonitrile at 60 degrees C if the soluble vanadium(v) salt, n-Bu4NVO3, is used as a catalyst. Alkyl hydroperoxides are formed as main products which decompose during the course of the reaction to produce the more stable corresponding alcohols and ketones. Turnover numbers (ie. numbers of moles of products per one mole of a catalyst) attained 250. The kinetics and selectivity of the reaction have been studied. The mechanism proposed involves the formation of a complex between the V(V) species and t-BuOOH (K5 was estimated to be 5 dm3 mol(-1)) followed by decomposition of this complex (k6 = 0.2 s(-1)). The generated V(IV) species reacts with another t-BuOOH molecule to produce an active t-BuO* radical which attacks the hydrocarbon.     

Aluminum phosphate dispersed on a cellulose acetate fiber surface: Preparation, characterization and application for Li, Na and K separation

Cellulose acetate fibers with supported highly dispersed aluminum phosphate were prepared by reacting aluminum-containing cellulose acetate (Al₂O₃=3.5 wt.%; 1.1 mmol g⁻¹ aluminum atom per gram of the material) with phosphoric acid. Solid-state NMR spectra (CPMAS ³¹P NMR) data indicated that HPO₄²⁻ is the species present on the fiber surface. The specific concentration of acidic centers, determined by ammonia gas adsorption, is 0.50 mmol g⁻¹. The ion exchange capacities for Li⁺, Na⁺ and K⁺ ions were determined from ion exchange isotherms at 298 K and showed the following values (in mmol g⁻¹): Li⁺=0.03, Na⁺=0.44 and K⁺=0.50. The H⁺/Li⁺ exchange corresponds to the model of the ideal ion exchange with a small value of the corresponding equilibrium constant K=1.1×10⁻². Due to the strong cooperative effect, the H⁺/Na⁺ and H⁺/K⁺ ion exchange is non-ideal. These ion exchange equilibria were treated with the use of models of fixed bi- or tridentate centers, which consider the surface of the sorbent as an assemblage of polyfunctional sorption centers. Both the observed ion exchange capacities with respect to the alkaline metal ions and the equilibrium constants were discussed by taking into consideration the sequence of the ionic hydration radii for Li⁺, Na⁺ and K⁺. The matrix affinity order for the ions decreases as the hydration radii of the cations increase, i.e. Li⁺>Na⁺>K⁺. The high values of the separation factors S_Na⁺/Li⁺ and S_K⁺/Li⁺ (up to several hundred) provide quantitative separation of Na⁺ and K⁺ from Li⁺ from a mixture containing these three ions.     

Macroscopic order and electro-optic response of dipolar chromophore-polymer materials.

This Minireview considers the key factors that govern the organization of macroscopic polarization in nonlinear optical systems obtained by electric poling of organic dipolar chromophores dissolved in polymer matrices. The macroscopic electric polarization depends on the thermodynamic state of the dipole system. The dependence of the paraelectric and antiferroelectric states of dipolar chromophores on the chromophore concentration and the strength of the poling field is discussed. Phase transitions between the para- and antiferroelectric states are investigated within the limits of the Ising and isotropic models for the chromophore dipoles and are considered for varying chromophore concentration, poling field strength, and macroscopic shape of the sample used for poling. The macroscopic polarization and electro-optic coefficient of the material change drastically upon phase transition. The theories are compared with the experimental data on the electro-optic coefficient dependence on the chromophore concentration. The isotropic dipole model shows excellent agreement with experiment for the chromophore systems most commonly used in nonlinear optics.     

Enhancement of frequency modulation response time for polymer-dispersed liquid crystal

Through the ferroelectric nanoparticles of BaTiO₃ (BTO) doping, the response time for the frequency modulation of the polymer-dispersed liquid crystal (PDLC) was improved. The BTO-doped PDLC cells were prepared by polymerisation induced phase separation (PIPS) process using UV light. The capacitance of the PDLC composites was measured with an impedance analyzer in the frequency range of 100 Hz–1 MHz at 1 V. The dynamic signal for the response time of the PDLC devices was monitored through a digital oscilloscope. The electro-optical properties of the PDLC were found to strongly depend on the doped BTO concentration. The BTO doping caused a large increase in the capacitance. The dielectric constants were drastically decreased in the samples with rather low BTO doping ratio at a high frequency. No outstanding difference in the rising time of the LC was observed in the BTO-doped PDLC device, but the falling time was significantly decreased from 0.334 to 0.094 s. The present results imply that the nanoparticle-doping technology could improve the electro-optical performance of the PDLC requiring fast response and frequency modulation, such as optical modulators and PDLC-hybrid electroluminescence device for flexible electronic devices.     

Thermoelasticity of thin shells based on the time-fractional heat conduction equation

The time-nonlocal generalizations of Fourier’s law are analyzed and the equations of the generalized thermoelasticity based on the time-fractional heat conduction equation with the Caputo fractional derivative of order 0 < α ≤ 2 are presented. The equations of thermoelasticity of thin shells are obtained under the assumption of linear dependence of temperature on the coordinate normal to the median surface of a shell. The conditions of Newton’s convective heat exchange between a shell and the environment have been assumed. In the particular case of classical heat conduction (α = 1) the obtained equations coincide with those known in the literature.     

One Step up the Ladder of Prebiotic Complexity: Formation of Nonrandom Linear Polypeptides from Binary Systems of Amino Acids on Silica

Evidence for the formation of linear oligopeptides with nonrandom sequences from mixtures of amino acids coadsorbed on silica and submitted to a simple thermal activation is presented. The amino acid couples (glutamic acid+leucine) and (aspartic acid+valine) were deposited on a fumed silica and submitted to a single heating step at moderate temperature. The evolution of the systems was characterized by X-ray diffraction, infrared spectroscopy, thermosgravimetric analysis, HPLC, and electrospray ionization mass spectrometry (ESI-MS). Evidence for the formation of amide bonds was found in all systems studied. While the products of single amino acids activation on silica could be considered as evolutionary dead ends, (glutamic acid+leucine) and, at to some extent, (aspartic acid+valine) gave rise to the high yield formation of linear peptides up to the hexamers. Oligopeptides of such length have not been observed before in surface polymerization scenarios (unless the amino acids had been deposited by chemical vapor deposition, which is not realistic in a prebiotic environment). Furthermore, not all possible amino acid sequences were present in the activation products, which is indicative of polymerization selectivity. These results are promising for origins of life studies because they suggest the emergence of nonrandom biopolymers in a simple prebiotic scenario.     

An efficient synthesis of multisubstituted 4-nitrobuta-1,3-dien-1-amines and application in cyclisation reactions

The synthesis of multisubstituted 4-nitrobuta-1,3-dien-1-amines (nitrodienamines) from 3-aminocrotonates and nitroacetaldehyde potassium salt, has been performed in 45–89% yields. This one-step protocol works efficiently with a broad range of N-H and N-substituted 3-aminocrotonates and delivers both primary and secondary nitrodienamines. In addition, the possible variations of the substituents at the positions 2 and 3 of 4-nitrobuta-1,3-dien-1-amine have been shown. Generally, the yields of secondary 4-nitrobuta-1,3-dien-1-amines were lower than those of primary ones. The synthetic usefulness of obtained 4-nitrobuta-1,3-dien-1-amines has also been demonstrated by achieving the synthesis of multisubstituted 5-nitro-1,6-dihydropyridines in two-component cyclocondensation reactions of 4-nitrobuta-1,3-dien-1-amines with aromatic or aliphatic aldehydes. Lastly, diverse N-H and N-substituted 5-nitro-1,6-dihydropyridines have been obtained in 35–87% yields.     

Effect of branching on the physical and photovoltaic properties of donor–acceptor oligomers based on triphenylamine

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