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).     

A dissipation‐free numerical method to solve one‐dimensional hyperbolic flow equations

In this paper, a numerical method to capture the shock wave propagation in 1‐dimensional fluid flow problems with 0 numerical dissipation is presented. Instead of using a traditional discrete grid, the new numerical method is built on a range‐discrete grid, which is obtained by a direct subdivision of values around the shock area. The range discrete grid consists of 2 types: continuous points and shock points. Numerical solution is achieved by tracking characteristics and shocks for the movements of continuous and shock points, respectively. Shocks can be generated or eliminated when triggering entropy conditions in a marking step. The method is conservative and total variation diminishing. We apply this new method to several examples, including solving Burgers equation for aerodynamics, Buckley‐Leverett equation for fractional flow in porous media, and the classical traffic flow. The solutions were verified against analytical solutions under simple conditions. Comparisons with several other traditional methods showed that the new method achieves a higher accuracy in capturing the shock while using much less grid number. The new method can serve as a fast tool to assess the shock wave propagation in various flow problems with good accuracy.     

A study into Stille cross‐coupling reaction mediated by palladium catalysts deposited over siliceous supports bearing N‐donor groups at the surface

Mesoporous molecular sieve SBA‐15 and conventional silica gel were grafted with 3‐[2‐(diethylamino)ethylamino]propyl groups and used as supports for the preparation of deposited palladium catalysts, which were subsequently evaluated in Stille cross‐coupling reaction of aryl bromides. The highest conversions were achieved with the metal‐saturated catalyst resulting from the modified SBA‐15. Influence of various reaction parameters (solvent, additive, temperature, etc.) on the overall yield and selectivity was studied. Copyright © 2013 John Wiley & Sons, Ltd.     

Poly(2‐oxazoline) hydrogels crosslinked with aliphatic bis(2‐oxazoline)s: Properties,cytotoxicity, and cell cultivation

A series of hydrogels from 2‐ethyl‐2‐oxazoline and three bis(2‐oxazoline) crosslinkers—1,4‐butylene‐2,2′‐bis(2‐oxazoline), 1,6‐hexamethylene‐2,2′‐bis(2‐oxazoline), and 1,8‐octamethylene‐2,2′‐bis(2‐oxazoline)—are prepared. The hydrogels differ by the length of aliphatic chain of crosslinker and by the percentage of crosslinker (2–10%). The influence of the type and the percentage of the crosslinker on swelling properties, mechanical properties, and state of water is studied. The equilibrium swelling degree in water ranges from 2 to 20. With a proper selection of the crosslinker, Young's modulus can be varied from 10 kPa to almost 100 kPa. To evaluate the potential for medical applications, the cytotoxicity of extracts and the contact toxicity toward murine fibroblasts are measured. The hydrogels with the crosslinker containing a shorter aliphatic exhibit low toxicity toward fibroblast cells. Moreover, the viability and the proliferation of pancreatic β‐cells incubated inside hydrogels for 12 days are analyzed. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1548–1559     

Physical properties (thermal,thermomechanical, magnetic,and adhesive) of some smart orthodontic wires

Thermal, thermomechanical, and caloric properties of commercial orthodontic wires (produced by Natural Orthodontics Corp., USA) with cylindrical and rectangular geometry were studied. Depending on the applied forces, there were identified the range of elasticity, the elasticity–viscoelasticity coexistence domain and the domain in which a maximum force of 18 N is applied, for the orthodontic wires. When increasing the thickness of orthodontic wires, deformation decreases. The Controlled Force Module, in the tension mode, was used for the determination of the orthodontic wires elongation at application of the stretching forces from 0 to 13 N, at 35 °C, maintaining each static force value for 3 min. The increase in the cross-sectional area of the orthodontic wires disfavors the process of elongation of the sample, at the same applied static force. Using the Multi-Frequency–Strain–Stress modulus, in the tension mode, DMA cyclic heating–cooling measurements were performed. The measured physical quantities for orthodontic wires were Storage Modulus, Loss Modulus, Tanδ and Stiffness, at heating and cooling. Thus, the characteristic temperatures of the phase transitions (A_s, A_f, M_s, M_f), of all the studied orthodontic wires were identified. Also, the values of the elasticity modulus (Young’s Modulus) of the orthodontic wires were calculated at 35 °C. With the DSC Q200 device, using temperature-modulated differential scanning calorimetry method, a multi-step temperature variation program, was applied to a rectangular wire, in three stages (cooling–heating–cooling). Through the interpretation of heat fluxes (reversible, irreversible and total), the phase transitions in the formation of martensite, austenite, but also of the rombohedral phase (R-phase), were identified. Formations of austenite and martensite were also evidenced by the classical DSC method, but the classical DSC method also enabled the R-phase identification. The adherence of some food dyes on the orthodontic wires, as well as the modification of the surface roughness of the orthodontic wire after the deposition of the food dye, was also studied. By magnetic measurements, it was established that the orthodontic wires had paramagnetic properties at room temperature, and nitinol was a mixture of 49.2% austenite and 50.8% martensite.

     

A Methodology for Temperature Correction When Using Two-Color Pyrometers - Compensation for Surface Topography and Material

In this investigation, the applicability of the two-color pyrometer technique for temperature measurements in dry hard turning of AISI 52100 steel was studied, where both machined surfaces as well as cutting tools were considered. The impacts of differing hard turned surface topography on the two-color pyrometer readings was studied by conducting temperature measurements on reference samples created using cutting tools with different degrees of tool flank wear. In order to conduct measurements in a controlled environment, a specially designed furnace was developed in which the samples were heated step-wise up to 1,000 °C in a protective atmosphere. At each testing temperature, the temperatures measured by the two-color pyrometer were compared with temperatures recorded by thermocouples. For all materials and surfaces as studied here, the two-color pyrometer generally recorded significantly lower temperatures than the thermocouples; for the hard turned surfaces, depending on the surface topography, the temperatures were as much as ~20 % lower and for the CBN cutting tools, ~13 % lower. To be able to use the two-color pyrometer technique for temperature measurements in hard turning of AISI 52100 steel, a linear approximation function was determined resulting in three unique equations, one for each of the studied materials and surfaces. By using the developed approximation function, the measured cutting temperatures can be adjusted to compensate for differing materials or surface topographies for comparable machining conditions. Even though the proposed equations are unique for the hard turning conditions as studied here, the proposed methodology can be applied to determine the temperature compensation required for other surface topographies, as well as other materials.