Stoichiometric and Catalytic Inter‐ and Intramolecular Hydroamination of Terminal Alkynes by Frustrated Lewis Pairs

Frustrated Lewis pairs (FLPs) based on sterically encumbered anilines and the Lewis acid B(C₆F₅)₃ were found to react with terminal alkynes effecting intermolecular hydroamination affording iminium alkynylborate species of the form [RPhN?C(R′)Me][R′CCB(C₆F₅)₃]. In these cases, the reagent ratio of borane, aniline, and alkyne is 1:1:2. These reactions could also be performed in an intramolecular fashion by using anilines with alkynyl substituents effecting cyclization reactions. The use of 10 mol % B(C₆F₅)₃ under a H₂ atmosphere provides a one‐pot synthesis of the pyrrolidine 12 , the piperidines 13 – 15 , the azepane 16 , the isoindoline 17 , and the benzoxazine 18 .     

Fuzzy model prediction of Co (III)Al2O3 catalytic behavior in Fischer-Tropsch synthesis

The application of Co(Ⅲ)/Al2O3 catalyst in Fischer-Tropsch synthesis(FTS)was studied in a wide range of synthesis gas conversions and compared with Fuzzy Simulation results.Present study applies fuzzy model to predicting the product composition of CH4,CO2 and CO in Fischer-Tropsch process for natural gas synthesis,in which the input vector was 4-dimension including four variables(operating pressure, operating temperature,time and CO/H2 ratio)of 70 different experiments and the output product is a composition of CO2,CO and CH4. The Mamdani algorithm has been applied to the training of the fuzzy system and the test set was used to evaluate the performance of the system including R2,ARE,AARE and SD.The results demonstrated that the predicted values from the model were in good consistency with the experimental data.The work indicates how fuzzy inference system(FIS),as a promising predicting technique,would be effectively used in FTS.     

Nuclear model calculation on charge particle induced reaction on Rb and Kr targets and targetry for 82Sr production

The ⁸²Sr/⁸²Rb radionuclide generator is used very commonly in positron emission tomography. ALICE/ASH and TALYS 1.0 codes were used to calculate excitation functions for proton, alpha and ³He induced on various targets that lead to produce ⁸²Sr radioisotope using intermediate energy accelerators. Recommended thickness of the targets according to SRIM code was premeditated. The application of those data, particularly in the calculation of integral yields, is discussed and theoretical integral yields for any reaction were computed. To consider precision of TALYS 1.0 code calculations, ⁸⁵Rb(p,4n)⁸²Sr process was determined as most interesting one due to radionuclide purity. The TALYS 1.0 code predicts a maximum cross-section of about 130 mb at 47 MeV for this reaction. Rubidium chloride deposition on copper substrate was carried out via sedimentation method in order to produce ⁸²Sr. 2.98 g RbCl, 1.043 g ethyl cellulose, 10 mL acetone were used to prepare a layer of enriched rubidium chloride of 11.69 cm² area and 0.34 g/cm² thickness.     

Observation of inductive effects that cause a change in the rate-determining step for the conversion of rhenium azides to imido complexes

The cationic oxorhenium(V) complex [Re(O)(hoz)(2)(CH(3)CN)][B(C(6)F(5))(4)] [1; Hhoz = 2-(2'-hydroxyphenyl)-2-oxazoline] reacts with aryl azides (N(3)Ar) to give cationic cis-rhenium(VII) oxoimido complexes of the general formula [Re(O)(NAr)(hoz)(2)][B(C(6)F(5))(4)] [2a-2f; Ar = 4-methoxyphenyl, 4-methylphenyl, phenyl, 3-methoxyphenyl, 4-chlorophenyl, and 4-(trifluoromethyl)phenyl]. The kinetics of formation of 2 in CH(3)CN are first-order in both azide (N(3)Ar) and oxorhenium(V) complex 1, with second-order rate constants ranging from 3.5 × 10(-2) to 1.7 × 10(-1) M(-1) s(-1). A strong inductive effect is observed for electron-withdrawing substituents, leading to a negative Hammett reaction constant ρ = -1.3. However, electron-donating substituents on phenyl azide deviate significantly from this trend. Enthalpic barriers (ΔH(?)) determined by the Eyring-Polanyi equation are in the range 14-19 kcal mol(-1) for all aryl azides studied. However, electron-donating 4-methoxyphenyl azide exhibits a large negative entropy of activation, ΔS(?) = -21 cal mol(-1) K(-1), which is in sharp contrast to the near zero ΔS(?) observed for phenyl azide and 4-(trifluoromethyl)phenyl azide. The Hammett linear free-energy relationship and the activation parameters support a change in the mechanism between electron-withdrawing and electron-donating aryl azides. Density functional theory predicts that the aryl azides coordinate via N(α) and extrude N(2) directly. For the electron-withdrawing substituents, N(2) extrusion is rate-determining, while for the electron-donating substituents, the rate-determining step becomes the initial attack of the azide. The barriers for these two steps are inverted in their order with respect to the Hammett σ values; thus, the Hammett plot appears with a break in its slope.     

Flow injection-based cloud point extraction of phosalone and ethion in seawater of Chabahar Bay and determination by high-performance liquid chromatography: study of use of carbon nanotube and nanofibers as a column filler in flow system

This study presents an easy and cost-effective flow-based cloud point extraction (CPE) method for determining partial amounts of two organophosphorus pesticides (phosalone and ethion) in seawater by HPLC–UV–Vis. In continues CPE methodology, the effect of the different column packing type such as carbon nanotube, polyacrylonitrile nanofiber and fiberglass on pesticide extraction was investigated. The Triton X-100 was utilized as nonionic surfactant, and moreover, effect of different parameters such as pH, temperature, extraction time, surfactant concentration, type and volume of the eluent solution on the extraction efficiency was optimized. Under optimum conditions, the figures of merit of the method for phosalone and ethion were obtained as: the enrichment factor (172 and 166), line range (0.8–300 and 0.5–300 µg L^?1, R ² = 0.9973 and 0.9982), relative standard deviation in concentration of 200 µg L^?1 (%RSD = %5.4 and %7.99, N = 5) and limit of detection (LOD = 0.24 and 0.14 µg L^?1). The suggested method was successfully used for determination of phosalone and ethion in Chabahar Bay seawaters with satisfactory results.     

Fast determination of Ziziphora tenuior L. essential oil by inorganic–organic hybrid material based on ZnO nanoparticles anchored to a composite made from polythiophene and hexagonally ordered silica

In this paper, for the first time, an inorganic–organic hybrid material based on ZnO nanoparticles was anchored to a composite made from polythiophene and hexagonally ordered silica (ZnO/PT/SBA-15) for use in solid-phase fibre microextraction (SPME) of medicinal plants. A homemade SPME apparatus was used for the extraction of volatile components of Ziziphora tenuior L. A simplex method was used for optimisation of five different parameters affecting the efficiency of the extraction. The main constituents extracted by ZnO/PT/SBA-15 and PDMS fibres and hydrodistillation (HD) methods, respectively, included pulegone (51.25%, 53.64% and 56.68%), limonene (6.73%, 6.58% and 8.3%), caryophyllene oxide (5.33%, 4.31% and 4.53%) and 1,8-cineole (4.21%, 3.31% and 3.18%). In comparison with the HD method, the proposed technique could equally monitor almost all the components of the sample, in an easier way, in a shorter time and requiring a much lower amount of the sample.