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1.
2.
The o-, m-, and p-phenylene bis(1,3-dioxolanium) dications (4-6) and 2,4,6-triphenylene tris(1,3-dioxolanium) trication (7) have been prepared by the ionization of the corresponding 2-methoxyethyl benzoates in FSO(3)H or CF(3)SO(3)H at 40 and 60 degrees C, respectively. The charge delocalization in these carbocations was probed by (13)C NMR chemical shifts and substantiated by GIAO/DFT calculations. Relatively less charge is delocalized into the aromatic ring of the carbotrication 7. The rotational barrier around the C(+)-Ar bond for carbodications 4 and 5 was also estimated to be 8-10 kcal/mol. 相似文献
3.
Michael P. Doyle Robert L. Dow Vahid Bagheri William J. Patrie 《Tetrahedron letters》1980,21(29):2794-2798
Oxidations of 2,2-disubstituted-1,4-butanediols by the combination of nickel(II) bromide and benzoyl peroxide and by trityl tetrafluoroborate produce β,β-disubstituted-γ-butyrolactones with exceptional selectivity. 相似文献
4.
A simple and environment friendly method was developed for determination of Malathion content of analytical and commercial insecticide samples with no special preparation. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectra were characterized and 1000-2000 cm−1 region was selected for quantitative analysis utilizing partial least square (PLS) and two wavelength selection methods: (a) principal component regression (PCR) and (b) genetic algorithm (GA). Relative error of prediction (REP) was calculated in PLS, PCR-PLS and GA-PLS methods and was 3.536, 1.656 and 0.188, respectively. Proposed method is successfully applicable for quantification of Malathion in commercial grade samples and reliable results in comparison with known methods, confirms this idea. 相似文献
5.
Rouhalla Bagheri Khirud B. Chakraborty Gerald Scott 《Journal of polymer science. Part A, Polymer chemistry》1984,22(7):1573-1578
When 4-hydroxy-2,2,6,6-tetramethyl piperidinoxyl (HTMPO) is processed in polypropylene in a closed mixer, almost 50% is converted to other products during the first few minutes whilst the applied torque in the mixer is high. There is associated formation of unsaturation and this fact, in conjunction with the almost complete regeneration of nitroxyl within five minutes, suggests that the corresponding hydroxylamine (HTMPOH), which can be qualitatively identified, is the major transformation product. A study of the UV stability of PP films fabricated from polymer processed for varying times shows that UV stability is related to the quantity of the redox couple (HTMPO + HTMPOH) remaining in the polymer. This is considerably reduced by severe processing. The redox capable has almost no thermal antioxidant (oven aging) activity. 相似文献
6.
The sorptive potential of sunflower stem (180-300 μm) for Cr(III) ions has been investigated in detail. The maximum sorption (≥85%) of Cr(III) ions (70.2 μM) has been accomplished using 30 mg of high density sunflower stem in 10 min from 0.001 M nitric and 0.0001 M hydrochloric acid solutions. The accumulation of Cr(III) ions on the sorbent follows Dubinin-Radushkevich (D-R), Freundlich and Langmuir isotherms. The isotherm yields D-R saturation capacity Xm = 1.60 ± 0.23 mmol g−1, β = −0.00654 ± 0.00017 kJ2 mol−2, mean free energy E = 8.74 ± 0.12 kJ mol−1, Freundlich sorption capacity KF = 0.24 ± 0.11 mol g−1, 1/n = 0.90 ± 0.04 and of Langmuir constant KL = 6800 ± 600 dm3 mol−1 and Cm = 120 ± 18 μmol g−1. The variation of sorption with temperature (283-323 K) gives ΔH = −23.3 ± 0.8 kJ mol−1, ΔS = −64.0 ± 2.7 J mol−1 K−1 and ΔG298k = −4.04 ± 0.09 kJ mol−1. The negative enthalpy and free energy envisage exothermic and spontaneous nature of sorption, respectively. Bisulphate, Fe(III), molybdate, citrate, Fe(II), Y(III) suppress the sorption significantly. The selectivity studies indicate that Cr(III), Eu(III) and Tb(III) ions can be separated from Tc(VII) and I(I). Sunflower stem can be used for the preconcentration and removal of Cr(III) ions from aqueous medium. This cheaper and novel sorbent has potential applications in analytical and environmental chemistry, in water decontamination, industrial waste treatment and in pollution abatement. A possible mechanism of biosorption of Cr(III) ions onto the sunflower stem has been proposed. 相似文献
7.
M. Rasul Jan Jasmin Shah Nadia Bashir 《International journal of environmental analytical chemistry》2013,93(1):27-35
Abstract A method for the dechlorination of PCB mixtures (Aroclor formulations) to biphenyl was extended to soils. The contaminated sample was mixed with magnesium flakes, potassium hexachloropalladiate (K2PdCl6), propan-2-ol and water then permitted to react for up to six hours. Biphenyl, recovered by extraction into hexane, was quantified by gas chromatography with flame ionization detection. The reaction was very efficient in propan-2-ol / water (~95%), surfactant emulsion or sand mixture and virtually complete in soil provided that excess magnesium (2 g) and the K2PdCl6 were added to the sample prior to the addition of water. Higher PCB loadings were readily determined in field contaminated soils either by direct determination within the matrix or by standard additions. However, analyte concentrations were appreciably over-estimated in Soxhlet or sonication extracts of a certified reference material that contained sub-ppm levels of analyte. The over-estimation is considered to result from the conversion in part of natural organic matter to biphenyl. 相似文献
8.
Following recent experimental works, herein we investigated chemical functionalization of a BN graphene-like sheet with hydrazine (N2H4) molecule based on the density functional theory. We found that the functionalization of the pristine sheet is not possible; while the presence of some structural defects such as Stone–Wales is essential to make it feasible. Functionalization energy of the defected sheet is calculated to be in the range of ?6.1 to ?7.4 kcal/mol at B3LYP/6-31G (d) level. Based on the obtained results, the functionalized BN sheet is found to be more soluble in water in comparison with the pristine sheet which is in good agreement with previous experimental reports. Also, it was found that the electronic properties of the defected sheet are slightly changed upon the chemical functionalization. 相似文献
9.
Z. Sanjabi Eznaveh M.H. Zahamtkesh A.R. Kamali Asl S. Bagheri 《Radiation measurements》2010,45(1):89-91
A new class of three-dimensional dosimeter (PRESAGE) has recently emerged, that consists of an optically clear polyurethane matrix containing a leuco dye and a free radical initiator. The dye exhibits a radiochromic response when exposed to ionizing radiation, changing color in proportion to the radiation dose. In this work we investigate and characterize the sensitivity of this new dosimeter by changing the portion of these two materials in the feature. Our results show considerable improvement in both dosimeter sensitivity and dose response stability by changing the percents of leuco dye and free radical initiator to approach to an optimum value. 相似文献
10.
Chemical functionalization of C60 fullerene with one to six carbene (CH2) molecule(s) has been investigated using density functional theory. We have found that the reaction is regioselective so that a CH2 molecule prefers to be adsorbed atop a C–C bond which is shared between two hexagonal rings of the C60, releasing energy of ?3.95 eV. Singly occupied molecular orbital (SOMO) of the CH2 interacts with LUMO of the C60 via a [2 + 1] cycloaddition reaction. Energy of the reaction and work function of the system are decreased by increasing the number of adsorbed CH2 molecules. The HOMO/LUMO energy gap of C60 is slightly changed and the electron emission from its surface is facilitated upon the functionalization. 相似文献