Kinetic studies of the reaction of phenacyl bromide derivatives with sulfur nucleophiles

The reaction of the substituted phenacyl bromides 1a–e and 2a–e with thioglycolic acid 3 and thiophenol 6 in methanol underwent nucleophilic substitution S_N2 mechanism to give the corresponding 2‐sulfanylacetic acid derivatives 4a–e, 5a–e and benzenethiol derivatives 9a–e, 10a–e. The reactants and products were identified by mass spectra, infrared and nuclear magnetic resonance. We measured the kinetics of these reactions conductometrically in methanol at a range of temperatures. The rates of the reactions were found to fit the Hammett equation and correlated with σ‐Hammett values. The ρ values for thioglycolic acid were 1.22–1.21 in the case of 4‐substituted phenacyl bromide 1a–e, while in the case of the nitro derivatives 2a–e they were 0.39–0.35. The ρ values for thiophenol were 0.97–0.83 in the case of 4‐substituted phenacyl bromide 1a–e, while in the case of the nitro derivatives 2a–e they were 0.79–0.74. The Brønsted‐type plot was linear with a α = ?0.41 ± 0.03. The kinetic data and structure‐reactivity relationships indicate that the reaction of 1a–e and 2a–e with thiol nucleophiles proceeds by a concerted mechanism. The plot of log k₄₅ versus log k₃₀, the plot log(k_x,3‐NO2/k_H) versus log(k_x/k_H), and the Brønsted‐type correlation indicate that the reactions of the thiol nucleophiles with the substituted phenacyl bromides 1a–e and 2a–e are attributed to the electronic nature of the substituents. Copyright © 2011 John Wiley & Sons, Ltd.     

New structures for closed-form wave solutions for the dynamical equations model related to the ion sound and Langmuir waves

This treatise analyzes the coupled nonlinear system of the model for the ion sound and Langmuir waves.The modified(G'/G)-expansion procedure is utilized to raise new closed-form wave solutions.Those solutions are investigated through hyperbolic,trigonometric and rational function.The graphical design makes the dynamics of the equations noticeable.It provides the mathematical foundation in diverse sectors of underwater acoustics,electromagnetic wave propagation,design of specific optoelectronic devices and physics quantum mechanics.Herein,we concluded that the studied approach is advanced,meaningful and significant in implementing many solutions of several nonlinear partial differential equations occurring in applied sciences.     

SOME SUBGROUPS OF THE EXTENDED HECKE GROUPS (H)(λq)

The authors consider the extended Hecke groups H(λq) generated by T(z) =-1 / z, S(z) = -1/(z+λq) and R(z) = 1 / -z with λq = 2cos(π/q) for q ≥ 3 an integer. Inthis paper, the even subgroup He(λq), the second commutator subgroup H"(λq) and theprincipal congruence subgroups Hp(λq) of the extended Hecke groups H(λq) are studied.Also, relations between them are given.     

Structure and effects of annealing in colloidal matrix‐free Ge quantum dots

The structure of small (2–5 nm) Ge quantum dots prepared by the colloidal synthesis route is examined. Samples were synthesized using either GeO₂ or GeCl₄ as precursor. As‐prepared samples were further annealed under Ar or H₂/Ar atmosphere at different temperatures in order to understand the effect of annealing on their structure. It was found that as‐prepared samples possess distinctly different structures depending on their synthesis route as indicated by their long‐range ordering. An appreciable amount of oxygen was found to be bound to Ge in samples prepared with GeO₂ as a precursor; however, not for GeCl₄. Based on combined transmission electron microscope, Raman, X‐ray diffraction and X‐ray absorption measurements, it is suggested that as‐prepared samples are best described by the core‐shell model with a small nano‐crystalline core and an amorphous outer layer terminated either with oxygen or hydrogen depending on the synthesis route. Annealing in an H₂Ar atmosphere leads to sample crystallization and further nanoparticle growth, while at the same time reducing the Ge—O bonding. X‐ray diffraction measurements for as‐prepared and annealed samples indicate that diamond‐type and metastable phases are present.     

Temperature dependent photoluminescence of PECVD a-SiOx:H (x<2)

The temperature dependent visible photoluminescence (PL) property of a-SiO_x:H (x<2) samples prepared in a PECVD system by using SiH₄+CO₂ gas mixture is investigated at a temperature range of 20 K-400 K. One of the two explicitly distinguished PL bands, with varying peak photon energies between 1.70 and 2.05 eV, can be detected at only low temperatures below 200 K, which is attributed to tail-to-tail radiative recombination. Thermal quenching parameter (T_L) of the tail-to-tail PL band is calculated as varying between 120 and 280 K as the atomic oxygen concentration ([O]at.%) of the samples increases. Stokes shift (ΔE_Stokes) of the tail-to-tail PL band is found to change from 85 meV to 420 meV due to band tail widening. The other PL band emerges at 2.1 eV and can be detected at higher temperatures with thermal activation behavior. The activation energies calculated about room temperature vary in the range of 8 meV-50 meV with oxygen concentration. Thermal activation of the 2.1 eV PL band is attributed to the behavior of thermally activated incoherent hopping migration of electrons. These electrons combine with self trapped holes (STHs) to form self trapped excitons (STEs). STEs are localized at intrinsic defects of SiO₂ structure such as oxygen vacancies (E′ centers) and non-bridging oxygen hole centers (NBOHC).     

Highway noise barrier perceived benefit

A laboratory experiment was performed in which 82 subjects judged the benefit of a noise barrier by listening to tape recordings of before-barrier and after-barrier traffic noise. These perceived benefit judgments were related by regression analysis to the barrier attenuation, the before-barrier traffic sound level, and a music background level, all of which were varied over the course of the experiment. Prediction equations were developed for barrier benefit in terms of these sound levels, their purpose being to provide a model for barrier benefit that can be used in barrier site selection and design. An unexpected finding was that barrier benefit was highest when before-barrier sound levels were lowest: i.e., subjects preferred a noise barrier that solved a moderate noise problem over an equally-attenuating barrier that only partially solved a more severe noise problem.     

Multi-solutions with specific geometrical wave structures to a nonlinear evolution equation in the presence of the linear superposition principle

Lump solutions are one of the most common solutions for nonlinear evolution equations.This study aspires to investigate the generalized Hietarintatype equation.We auspiciously provide multiple M-lump waves.On the other hand,collision phenomena to multiple M-lump waves with soliton wave solutions are also provided.During the collision,the amplitude of the lump will change significantly over the processes,whereas the amplitude of the soliton will just minimally alter.As it is of paramount importan...     

Classical Description of Two-Cluster Transfer Reactions in a Coulomb Field

The theory of two-cluster transfer reactions is reconsidered on the basis of a simple semiclassical approximation. The obtained expression for the differential cross section is in a closed form so as to be easily calculated. A theoretical study with calculations for the angular distribution for different incoming and outgoing energies, and also for different angular momentum transfer is introduced. Comparing our theoretical calculations with experimental data, satisfactory agreement is obtained especially in the backward direction.     

Short-range correlations with pseudopotentials. IV

Using a unitary model operator, the short-range correlations between nucleons in nuclei have been considered. To achieve healing in the wave functions, short-range pseudopotentials are required to be added to the nucleon-nucleon potential. With the introduction of the pseudopotentials, the matrix element for the effective interaction in nuclei is developed with correlated basis wave functions. The tensor forces and the short-range pseudopotentials are renormalized in second-order perturbation theory. Hartree-Fock calculations are carried out for the two finite closed-shell spherical nuclei¹⁶O and⁴⁰Ca. The calculations of the resulting effective Hamiltonian are carried out with an effective interaction derived from the Tabakin potential. The present calculations of the binding energies per particle for the¹⁶O and⁴⁰Ca nuclei are in agreement with the experimental measurements.     

Nucleon-nucleon interaction in the three-nucleon system

The three-nucleon system is reconsidered. The Faddeev equations are given leading to a set of integral equations. Solving these integral equations, suitable forms are considered for the nucleon-nucleon interaction. In the bound state of three-nucleon system, the form of the nuclear forces from the nucleon-nucleon interaction is important. In the present calculations, we consider the nuclear forces resulting from the nucleon-nucleon interaction by the exchange of a scalar meson, a pseudoscalar meson, and a massless vector meson. With this different meson exchange nucleon-nucleon interaction, the binding energy of the three-nucleon system is calculated by solving the Faddeev integral equations giving a value of 8.452 MeV.