Multi-State Second-Order Nonlinear Optical Switches Incorporating One to Three Benzazolo-Oxazolidine Units: A Quantum Chemistry Investigation

This contribution employs quantum chemistry methods to describe the variations of the second nonlinear optical responses of molecular switches based on benzazolo-oxazolidine (BOX) units, connected by π-linkers, along their successive opening/closing. Under the fully closed forms, all of them display negligible first hyperpolarizability (β) values. When one BOX is opened, which is sketched as C→O, a push–pull π-conjugated segment is formed, having the potential to enhance β and to set the depolarization ratio (DR) to its one-dimensional-like value (DR = 5). This is observed when only one BOX is open, either for the monoBOX species (C→O) or for the diBOX (CC→CO) and triBOX (CCC→CCO) compounds, i.e., when the remaining BOXs stay closed. The next BOX openings have much different effects. For the diBOXs, the second opening (CO→OO) is associated with a decrease of β, and this decrease is tuned by controlling the conformation of the π-linker, i.e., the centrosymmetry of the whole compound because β vanishes in centrosymmetric compounds. For the triBOXs, the second opening gives rise to a Λ-shape compound, with a negligible change of β, but a decrease of the DR whereas, along the third opening, β remains similar and the DR decreases to the typical value of octupolar systems (DR = 1.5).     

Access to nonisocyanate poly(thio)urethanes: A comparative study

This article describes the synthesis of new cyclic compounds able to react with amines to get nonisocyanate polyurethanes (NIPUs). The contribution of the most studied five‐membered cyclic carbonate was compared to five‐membered cyclic dithiocarbonate analogous and to a six‐membered cyclic carbonate. Difunctional reactive species were obtained by a simple substitution reaction or an efficient thiol–ene coupling reaction. The products, obtained with high yields, were characterized by 1H NMR, 13C NMR, and Fourier tansform infrared spectroscopy analysis. The dicyclocarbonates were then used to synthesize NIPUs by step growth polymerization with several diamines. These materials exhibited glass transition temperatures from 19 to ?29 °C, molar mass from 1800 to 20,400 g mol^?1, and a 20% mass loss temperature (T_d = 20%) between 249 and 296 °C. Such materials are interesting candidates for coating applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3284–3296     

Regiospecific synthesis of cepanolide,a cancer chemoprotective micronutrient found in green onions

The naturally occurring γ-hydroxy-β-sulfanylbutenolide cepanolide and a range of new analogues were synthesized in concise, regiospecific manner through the combined use of 2-silyloxyfuran oxyfunctionalization and tandem thio-Michael addition/elimination.     

Study of Temperature and UV Wavelength Range Effects on Degradation of Photo-Irradiated Polyethylene Films Using DMA

Plastic bags mostly made of polyethylene (PE) cause pollution as solid waste due to their non-degradability nature. Initiation of a degradative process by enhanced photo-oxidation is a possible method for an accelerated degradation. This paper presents temperature treatment effects on PE films where photodegradation was initiated using ultraviolet (UV) irradiation in the ranges of 200–300 nm and 300–400 nm for 2 hr. Effects of temperature of 40°C and 55°C on non-UV-irradiated and UV-irradiated PE films processed by conventional methods were investigated and evaluated after 50 hr, 150 hr, and 350 hr of temperature exposure. The effects of UV wavelength range irradiation on the degradation were deduced. Measuring the dynamic moduli using a dynamic mechanical analyzer monitored the degradation. The decrease in average storage modulus was 62% with treatment at 55°C, higher than the 16% drop at 40°C for unirradiated samples after 350-hr exposure. Cross-linking in UV-exposed samples, characterized by an increase in dynamic modulus (stiffening), was observed followed by a reduction of storage modulus. Temperature treatment at 55°C together with 300–400-nm UV range irradiation resulted in the largest increase, i.e., 22% after 150 hr, followed by the largest reduction of storage modulus, i.e., 74.6% for a cumulative 350-hr exposure.     

Deviations from perfect memory in spin glass temperature cycling experiments

We study the deviations from perfect memory in negative temperature cycle spin glass experiments. It is known that the a.c. susceptibility after the temperature is raised back to its initial value is superimposed to the reference isothermal curve for large enough temperature jumps ΔT (perfect memory). For smaller ΔT, the deviation from this perfect memory has a striking non monotonous behavior: the `memory anomaly' is negative for small ΔT's, becomes positive for intermediate ΔT's, before vanishing for still larger ΔT's. We show that this interesting behavior can be reproduced by simple Random Energy trap models. We discuss an alternative interpretation in terms of droplets and temperature chaos. Received 23 May 2002 Published online 14 October 2002 RID="a" ID="a"e-mail: sasaki@ipno.in2p3.fr     

Representation surfaces of Young''s modulus and Poisson''s ratio for BCC transition metals

 The general expressions for the compliance , Young's modulus E(h k l) and Poisson's ratio υ(h k l) along an arbitrary direction [h k l] are given for cubic crystals. The representation surfaces, for which the length of the radius vector in the [h k l] direction equals to E(h k l) or υ(h k l), are constructed for seven BCC transition metals Cr, Fe, Mo, Nb, Ta, V and W. Neglecting W, which is isotropic, both representation surfaces of Young's modulus and Poisson's ratio are spherical surfaces. The remaining BCC transition metals may be grouped into two classes. In the first group (Cr, Mo, Nb and V) with negative values of s_A, Young's modulus surface has eight depressed corners and six rounded protuberances at the centers of the faces. In the second group (Fe and Ta) with positive values of s_A, on the contrary, Young's modulus surface has eight rounded protuberance corners and six depressions at the centers of the faces. The contrary conclusions are obtained for Poisson's ratio.     

Finite-time synchronization for a class of chaotic and hyperchaotic systems via adaptive feedback controller

This Letter investigates chaos synchronization of chaotic and hyperchaotic systems. Based on finite-time stability theory, a simple adaptive control method for realizing chaos synchronization in a finite time is proposed. In comparison with previous methods, the present method is not only simple, but could also be easily utilized in application. Numerical simulations are given to illustrate the effectiveness and validity of the proposed approach.     

Breather Solutions in Periodic Media

For nonlinear wave equations existence proofs for breathers are very rare. In the spatially homogeneous case up to rescaling the sine-Gordon equation \({\partial^2_t u = \partial^2_x u - \sin (u)}\) is the only nonlinear wave equation which is known to possess breather solutions. For nonlinear wave equations in periodic media no examples of breather solutions have been known so far. Using spatial dynamics, center manifold theory and bifurcation theory for periodic systems we construct for the first time such time periodic solutions of finite energy for a nonlinear wave equation

$ s(x) \partial^2_t u(x,t) = \partial^2_x u(x,t) - q(x) u(x,t)+ r(x)u(x,t)^3, $

with spatially periodic coefficients s, q, and r on the real axis. Such breather solutions play an important role in theoretical scenarios where photonic crystals are used as optical storage.