One‐Pot Synthesis of Sulfonamides and Sulfonyl Azides from Thiols using Chloramine‐T

A convenient synthesis of sulfonamides and sulfonyl azides from thiols is described. In situ preparation of sulfonyl chlorides from thiols was accomplished by oxidation with chloramine‐T (=N‐chlorotosylamide=N‐chloro‐4‐methylbenzenesulfonamide), tetrabutylammonium chloride (Bu₄NCl), and H₂O. The sulfonyl chlorides were then further allowed to react with excess amine or NaN₃ in the same pot.     

The Role of Spin in Entanglement Generated by Expanding Spacetime

We investigate the effects of spin on entanglement arising in Dirac field in an expanding spacetime characterized by the Robertson-Walker metric. We present a general approach that allows us to treat the case where only charge conservation is required, as well as the case where also angular momentum conservation is required. We find that in both situations entanglement originated from the vacuum and quantified by subsystem entropy behaves the same and does not qualitatively deviates from the spinless case. Differences only arise when particles and/or antiparticles are present in the input state.     

Ab initio study of atropisomers of derivatives of 1,8-di-pyridine 9H-fluorene, dibenzo[b,d]furan, 9H-carbazole and dibenzo[b,d]thiophene

Ab initio calculation at HF/6-31G^* and MP2/6-31G^* levels of theory for geometry optimization of some syn- and anti-1,8-di-pyridine 9H-fluorene, dibenzo[b,d]furan, 9H-carbazole and Dibenzo[b,d]thiophene are reported. The rotational barrier energy, heat of formation and Gibbs energy are determined for the conversion of the anti-(syn) to the syn (anti)-isomers at 25 °C in the gas phase. The models are chosen as isomers of 9H-fluorene, dibenzo[b,d]furan, 9H-carbazole and dibenzo[b,d]thiophene as scaffold with pyridine as module. Results obtained show that (at equilibrium) for most of atropisomers the syn- is favored over the anti-isomer. Moreover, the ground state structures show that the modules are not parallel to each other but are tilted away in order to increase separation and there by minimize electrostatic repulsion. In atropisomers of 9H-carbazole the isomers are showing an attraction due to the presence of nitrogen atom. Influence of the position of nitrogen atom on the magnitude of the rotational barriers in these atropisomers is also studied.     

Electrochemical synthesis of 6-amino-5-(3,4-dihydroxyphenyl) pyrimidine

Electrochemical oxidation of several catechols is studied in the presence of 4(6)-aminouracil (3a) and 6-amino-1,3-dimethyl uracil (3b) as nucleophiles in aqueous solution using cyclic voltammetry and controlled-potential coulometry. The results reveal that quinones derived from catechols participate in Michael additions with 3a and 3b to give the corresponding catecholamine derivatives via an electron transfer followed by chemical reaction (EC) mechanistic pathway in good yields and purities.     

RKM for solving Bratu‐type differential equations of fractional order

The purpose of the present paper is to propose an efficient numerical method for solving the differential equations of Bratu‐type with fractional order in reproducing kernel Hilbert space. The exact solution is calculated in the form of a convergent series with easily computable components. Finally, some examples are given to illustrate the efficiency and applicability of the method. Copyright © 2015 John Wiley & Sons, Ltd.     

Nano‐structured gemini‐based supramolecular solvent for the microextraction of cyhalothrin and fenvalerate

A novel supramolecular solvent‐based microextraction followed by high‐performance liquid chromatography with ultraviolet detection method has been developed for the extraction and determination of two pyrethroid analytes, cyhalothrin and fenvalerate, in water and soil samples. The liquid–liquid‐phase separation of surfactants has been used in analytical extraction. The surfactant‐rich phase is a nano‐structured liquid, recently named as a supramolecular solvent, generated from the amphiphiles. The alkyl carboxylic acid based supramolecular solvents were introduced before. Coacervates made up of gemini surfactant, consisting of two amphiphilic moieties, were first used as solvent. The effective parameters on extraction (i.e., type of organic solvent, the amount of surfactant and volume of tetrahydrofuran, sample solution pH, salt addition, ultrasonic and centrifugation time) were investigated and optimized. Under the optimum conditions, preconcentration factors of 110 and 145 were obtained for the analytes. The linearity was 0.5–200.0 μg/L with the correlation of determination of (R²) ≥ 0.9984. The limit of detection of the method was (S/N = 3) 0.2 μg/L, and precisions in the range of 6.3–10.3% (RSDs, n = 5) were obtained. This method has been successfully applied to analyze real samples, and good recoveries in the range of 101.2–108.8% were obtained.     

Supramolecular-based solvent microextraction of carbaryl in water samples followed by high performance liquid chromatography determination

In this study, a simple, rapid, low cost, sensitive and environmentally friendly technique, supramolecular solvent microextraction (SM-SME) followed by high performance liquid chromatography-ultraviolet has been proposed to extract carbaryl from water samples. Parameters, affecting the SM-SME performance such as the weight of decanoic acid (DeA), volume of tetrahydrofuran (THF), pH and salt concentration, were studied and optimised. The effect of the pH on the extraction efficiency was evaluated by one–factor-at-a-time methodology, but the other variables were optimised by a face-centred cube central composite design methodology. Optimum extraction conditions were obtained: DeA: 70 mg; THF: 650 µL; salt concentration: 10% (w/v) NaCl and pH = 2–4), and the performance of the proposed method was evaluated. Under the optimum conditions, good linearity (1.0–500 µg L^?1, r² = 0.9994) was obtained. Limit of detection and limit of quantification were 0.3–1.0 µg L^?1, respectively. Also, the recoveries of the carbaryl were obtained in the ranged from 96% to 105%. Finally, proposed method was successfully applied for the determination of the carbaryl in the water samples of farms run-off and rivers and satisfactory results were obtained.     

Interaction of isoniazid drug with the pristine and Ni-doped of (4, 4) armchair GaNNTs: a first principle study

In this research, the interaction of isoniazid drug (INH) with the pristine and Ni-doped Gallium nitride nanotubes (GaNNTs) is investigated by using density function theory. The adsorption energy, deformation energy, natural bond orbital (NBO), quantum parameters, molecular electrostatic potential (MEP) and thermodynamic parameters of all adsorption models are calculated from optimized structures. The values of adsorption energy, enthalpy and Gibbs free energy of all adsorption models are negative and all adsorption process are favorable in view of thermodynamic points. It is notable that Ni-doped decrease adsorption strength and it is not suitable for INH adsorption on the GaNNTs surface. The MEP, NBO and maximum amount of electronic charge ΔN results demonstrate that the negative potential are localized around adsorption position and the positive potential are localized around INH molecule. The calculated results indicate that the GaNNTs is a good candidate to making absorber and sensor for detecting INH drug.     

Variational approaches to p-Laplacian discrete problems of Kirchhoff-type

Critical point results for Kirchhoff-type discrete boundary value problems are exploited in order to prove that a suitable class possesses at least one solution under an asymptotical behaviour of the potential of the nonlinear term at zero, and also possesses infinitely many solutions under some hypotheses on the behaviour of the potential of the nonlinear term at infinity. Some recent results are extended and improved. Some examples are presented to demonstrate the applications of our main results.