Abstract. An all-sky imager was installed in Asmara, Eritrea (15.4 • N, 38.9 • E, 7 • N dip) and used to monitor the OI 630-nm nightglow. Nine months of data were studied between September 2001 and May 2002, a time including the recent maximum in the solar activity cycle. Equatorial plasma bubbles (EPBs) were recorded on 63% of nights with adequate viewing conditions. The station location within view of the equatorial ionization anomaly and with a magnetic declination near zero makes it an excellent test case for comparison with satellite studies of the seasonal variation of EPBs with longitude. The imager was accompanied by two Cornell GPS scintillation monitors, and the amplitude scintillation data are compared to the all-sky data. GPS scintillations indicate the beginning of EPBs, but die out sooner in the post-midnight period than the larger scale EPBs. Both phenomena exhibit clear occurrence maxima around the equinoxes. Ionospheric zonal drift speeds have been deduced from EPB and GPS scintillation pattern movement. Average near-midnight EPB drift speeds are between 100 and 120 m/s most months, with the GPS scintillation speeds being about the same. A winter drift speed maximum is evident in both EPB and GPS scintillation monthly means.
The reactions of CuX2 (X = Cl, Br) with dipinodiazafluorenes yielded four new complexes [CuX2L1]2 (X = Cl (1), Br (2), L1 = (1R,3R,8R,10R)-2,2,9,9-Tetramethyl-3,4,7,8,9,10-hexahydro-1H-1,3:8,10-dimethanocyclopenta [1,2-b:5,4-b’]diquinolin-12(2H)-one) and [(CuX2)2L2]n (X = Cl (3), Br (4), L2 = (1R,3R,8R,10R,1’R,3’R,8’R,10’R)-2,2,2’,2’,9,9,9’,9’-Octamethyl-1,1’,2,2’,3,3’,4,4’,7,7’,8,8’,9,9’,10,10’-hexadecahydro-1,3:1’,3’:8,10:8’,10’-tetramethano-12,12’-bi(cyclopenta [1,2-b:5,4-b’]diquinolinylidene). The complexes were characterized by IR and EPR spectroscopy, HR-ESI-MS and elemental analysis. The crystal structures of compounds 1, 2 and 4 were determined by X-ray diffraction (XRD) analysis. Complexes 1–2 have a monomeric structure, while complex 4 has a polymeric structure due to additional coordinating N,N sites in L2. All complexes contain a binuclear fragment {Cu2(μ-X)2×2} (X = Cl, Br) in their structures. Each copper atom has a distorted square-pyramidal coordination environment formed by two nitrogen atoms and three halogen atoms. The Cu-Nax distance is elongated compared to Cu-Neq. The EPR spectra of compounds 1–4 in CH3CN confirm their paramagnetic nature due to the d9 electronic configuration of the copper(II) ion. The magnetic properties of all compounds were studied by the method of static magnetic susceptibility. For complexes 1 and 2, the effective magnetic moments are µeff ≈ 1.87 and 1.83 µB (per each Cu2+ ion), respectively, in the temperature range 50–300 K, which are close to the theoretical spin value (1.73 µB). Ferromagnetic exchange interactions between Cu(II) ions inside {Cu2(μ-X)2X2} (X = Cl, Br) dimers (J/kB ≈ 25 and 31 K for 1 and 2, respectively) or between dimers (θ′ ≈ 0.30 and 0.47 K for 1 and 2, respectively) were found at low temperatures. For compounds 3 and 4, the magnetic susceptibility is well described by the Curie–Weiss law in the temperature range 1.77–300 K with µeff ≈ 1.72 and 1.70 µB for 3 and 4, respectively, and weak antiferromagnetic interactions (θ ≈ −0.4 K for 3 and −0.65 K for 4). Complexes 1–4 exhibit high catalytic activity in the oxidation of alkanes and alcohols with peroxides. The maximum yield of cyclohexane oxidation products reached 50% (complex 3). Based on the data on the study of regio- and bond-selectivity, it was concluded that hydroxyl radicals play a decisive role in the oxidation reaction. The initial products in reactions with alkanes are alkyl hydroperoxides.
Two new isomeric complexes [CuBr2(R-bian)] (R = 4-Me-Ph (1), 2-Me-Ph (2)) were obtained by reacting copper(II) bromide with 1,2-bis[(2-methylphenyl)imino]acenaphthene ligands and characterized. The crystal structure of 2 was determined by X-ray diffraction analysis. The copper atom has a distorted square-planar environment; the ω angle between the CuN2 and CuBr2 planes is 37.004°. The calculated ω parameters for optimized structures 1 and 2 were 76.002° and 43.949°, indicating significant deviations from the ideal tetrahedral and square-plane geometries, respectively. Molecules 2 form dimers due to non-covalent Cu···Br contacts, which were analyzed by DFT calculations. The complexes were also characterized by cyclic voltammetry and UV-Vis spectroscopy. A quasi-reversible Cu(II)/Cu(I) redox event with E1/2 potentials of 0.81 and 0.66 V (vs. SHE) was found for 1 and 2, respectively. The electronic absorption spectra showed the presence of Cu(I) species as a result of the partial reduction of the complexes in the acetonitrile solution. Both complexes were tested as homogenous catalysts for the oxidation of isopropylbenzene (IPB) in acetonitrile at low temperatures. Differences in the mechanism of the catalytic reaction and the composition of the reaction products depending on the oxidizing ability of the catalyst were revealed.
Capillary electrophoresis (CE) has been developed as one of the powerful separation techniques for the analysis of inorganic and organic ions in complex matrices in the recent past. In aqueous samples, most of the inorganic ions are having weak absorption profiles in the UV-Vis region of the spectrum. These low absorption profile ionic species are commonly detected by indirect UV absorbance with the addition of an absorbing co-ion (chromophore) into the electrolyte. The inorganic cations oftenly require an additional complexing agent to selectively alter their similar mobilities and proper separation. The indirect detection at 214 nm was performed with α-hydroxyisobutyric acid (α-HIBA)-4-aminopyridine background electrolyte (BGE) that has a characteristic absorbance at 214 nm. The BGE was applied for the separation, analysis, and validation of metal ions in water samples. The metal ions such as K+, Na+, Ca2+, Mg2+, Mn2+, Fe2+, Cd2+, Pb2+, Ni2+ and Zn2+ were separated successfully in this study. Also, the effect of electrolyte pH, applied voltage and injection time for the separation of cations was investigated.
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