The effect of charged axial ligands on the EPR parameters in oxovanadium(IV) compounds: an unusual reduction of the Az (51V) values

Two series of octahedral oxovanadium(IV) compounds, containing charged or neutral axial ligands, with the tetradentate amidate molecules Hcapca and H2capcah of the general formulae trans-[V(IV)OX(capca)]0/+ (where X = Cl- (1.CH2Cl2), SCN- (2), N3 (3), CH3COO- (4), PhCOO- (5), imidazole (6. CH3NO2), and eta-nBuNH2 (7)) and cis-[V(VI)OX(Hcapcah)]0/+ (where X = Cl- (8.0.5CH2Cl2), SCN (9), N3 (10.2CH3OH), and imidazole (11)), were synthesized and characterized by X-ray crystallography (1.CH3OH,8.CHCl3, 9.2CH3CN, 10.CH3CN and cis-[VO(imidazole)(Hcapcah)+) and continuous-wave electron paramagnetic resonance (cw EPR) spectroscopy. In addition to the synthesis, crystallographic and EPR studies, the optical, infrared and magnetic properties (room temperature) of these compounds are reported. Ab initio calculations were also carried out on compound 8 CHCl3 and revealed that this isomer is more stable than the trans isomer, in good agreement with the experimental data. The cw EPR studies of compounds 1-5, that is, the V(IV)O2+ species containing monoanionic axial ligands, revealed a novel phenomenon of the reduction of their A, components by about 10% relative to the N4 reference compounds ([V(IV)O-(imidazole)4]2+ and [V(IV)O(2,2-bipyridine)2]2+). In marked contrast, such a reduction is not observed in compounds 6. CH3NO2-11, which contain neutral axial ligands. Based on the spin-Hamiltonian formalism a theoretical explanation is put forward according to which the observed reduction of Az is due to a reduction of the electron - nuclear dipolar coupling (P). The present findings bear strong relevance to cw EPR studies of oxovanadium(IV) in vanadoproteins, V(IV)O2+-substituted proteins, and in V(IV)O2+ model compounds, since the hyperfine coupling constant, Az, has been extensively used as a benchmark for identification of equatorial-donor-atom sets in oxovanadium(IV) complexes.     

Monomeric oxovanadium(IV) compounds of the general formula cis-[V(IV)(=O)(X)(L(NN))(2)](+/0) [X = OH(-), Cl(-), SO(4)(2)(-) and L(NN) = 2,2'-bipyridine (bipy) or 4,4'-disubstituted bipy

Reaction of [V(IV)OCl(2)(THF)(2)] in aqueous solution with 2 equiv of AgBF(4) or AgSbF(6) and then with 2 equiv of 2,2'-bipyridine (bipy), 4,4'-di-tert-butyl-2,2'-bipyridine (4,4'-dtbipy), or 4,4'-di-methyl-2,2'-bipyridine (4,4'-dmbipy) affords compounds of the general formula cis-[V(IV)O(OH)(L(NN))(2)]Y [where L(NN) = bipy, Y = BF(4)(-) (1), L(NN) = 4,4'-dtbipy, Y = BF(4)(-) (2.1.2H(2)O), L(NN) = 4,4'-dmbipy, Y = BF(4)(-) (3.2H(2)O), and L(NN) = 4,4'-dtbipy, Y = SbF(6)(-) (4)]. Sequential addition of 1 equiv of Ba(ClO(4))(2) and then of 2 equiv of bipy to an aqueous solution containing 1 equiv of V(IV)OSO(4).5H(2)O yields cis-[V(IV)O(OH)(bipy)(2)]ClO(4) (5). The monomeric compounds 1-5 contain the cis-[V(IV)O(OH)](+) structural unit. Reaction of 1 equiv of V(IV)OSO(4).5H(2)O in water and of 1 equiv of [V(IV)OCl(2)(THF)(2)] in ethanol with 2 equiv of bipy gives the compounds cis-[V(IV)O(OSO(3))(bipy)(2)].CH(3)OH.1.5H(2)O (6.CH(3)OH.1.5H(2)O) and cis-[V(IV)OCl(bipy)(2)]Cl (7), respectively, while reaction of 1 equiv of [V(IV)OCl(2)(THF)(2)] in CH(2)Cl(2) with 2 equiv of 4,4'-dtbipy gives the compound cis-[V(IV)OCl(4,4'-dtbipy)(2)]Cl.0.5CH(2)Cl(2) (8.0.5CH(2)Cl(2)). Compounds cis-[V(IV)O(BF(4))(4,4'-dtbipy)(2)]BF(4) (9), cis-[V(IV)O(BF(4))(4,4'-dmbipy)(2)]BF(4) (10), and cis-[V(IV)O(SbF(6))(4,4'-dtbipy)(2)]SbF(6) (11) were synthesized by sequential addition of 2 equiv of 4,4'-dtbipy or 4,4'-dmbipy and 2 equiv of AgBF(4) or AgSbF(6) to a dichloromethane solution containing 1 equiv of [V(IV)OCl(2)(THF)(2)]. The crystal structures of 2.1.2H(2)O, 6.CH(3)OH.1.5H(2)O, and 8.0.5CH(2)Cl(2) were demonstrated by X-ray diffraction analysis. Crystal data are as follows: Compound 2.1.2H(2)O crystallizes in the orthorhombic space group Pbca with (at 298 K) a = 21.62(1) A, b = 13.33(1) A, c = 27.25(2) A, V = 7851(2) A(3), Z = 8. Compound 6.CH(3)OH.1.5H(2)O crystallizes in the monoclinic space group P2(1)/a with (at 298 K) a = 12.581(4) A, b = 14.204(5) A, c = 14.613(6) A, beta = 114.88(1) degrees, V = 2369(1), Z = 4. Compound 8.0.5CH(2)Cl(2) crystallizes in the orthorhombic space group Pca2(1) with (at 298 K) a = 23.072(2) A, b = 24.176(2) A, c = 13.676(1) A, V = 7628(2) A(3), Z = 8 with two crystallographically independent molecules per asymmetric unit. In addition to the synthesis and crystallographic studies, we report the optical, infrared, magnetic, conductivity, and CW EPR properties of these oxovanadium(IV) compounds as well as theoretical studies on [V(IV)O(bipy)(2)](2+) and [V(IV)OX(bipy)(2)](+/0) species (X = OH(-), SO(4)(2)(-), Cl(-)).     

Narrow band quantitative and multivariate electroencephalogram analysis of peri-adolescent period

ABSTRACT: BACKGROUND: The peri-adolescent period is a crucial developmental moment of transition from childhood to emergent adulthood. The present report analyses the differences in Power Spectrum (PS) of the Electroencephalogram (EEG) between late childhood (24 children between 8 and 13 years old) and young adulthood (24 young adults between 18 and 23 years old). RESULTS: The narrow band analysis of the Electroencephalogram was computed in the frequency range of 0--20 Hz. The analysis of mean and variance suggested that six frequency ranges presented a different rate of maturation at these ages, namely: low delta, delta-theta, low alpha, high alpha, low beta and high beta. For most of these bands the maturation seems to occur later in anterior sites than posterior sites. Correlational analysis showed a lower pattern of correlation between different frequencies in children than in young adults, suggesting a certain asynchrony in the maturation of different rhythms. The topographical analysis revealed similar topographies of the different rhythms in children and young adults. Principal Component Analysis (PCA) demonstrated the same internal structure for the Electroencephalogram of both age groups. Principal Component Analysis allowed to separate four subcomponents in the alpha range. All these subcomponents peaked at a lower frequency in children than in young adults. CONCLUSIONS: The present approaches complement and solve some of the incertitudes when the classical brain broad rhythm analysis is applied. Children have a higher absolute power than young adults for frequency ranges between 0-20 Hz, the correlation of Power Spectrum (PS) with age and the variance age comparison showed that there are six ranges of frequencies that can distinguish the level of EEG maturation in children and adults. The establishment of maturational order of different frequencies and its possible maturational interdependence would require a complete series including all the different ages.     

Dissociations of Complexes Between Monovalent Metal Ions and Aromatic Amino Acid or Histidine

The fragmentations of [AA + M]⁺ complexes, where AA = Phe, Tyr, Trp, or His, and M is a monovalent metal (Li, Na, or Ag), have been exhaustively studied through collision-induced dissociation (CID) and through deuterium labeling. Dissociations of the Li- and Ag-containing complexes gave a large number of fragment ions; by contrast, the sodium/amino acid complexes have lower binding energies, and dissociation resulted in much simpler spectra, with loss of the entire ligand dominating. Unambiguous assignments of these fragment ions were made and formation mechanisms are proposed. Of particular interest are fragmentations in which the charge was retained on the organic fragment and the metal was lost, either as a metal hydride (AgH) or hydroxide (LiOH) or as the silver atom (Ag^?).

Chemical characterization of particulate matter (PM) and source apportionment study during winter and summer period for the city of Kozani,Greece

Eordaia basin located in northwest of Greece, comprises an area which is characterized by intense energy related activities, including coal burning at four power plants and the associated mining operations. Air samples of inhalable (PM10) and respirable particles (PM2.5) were collected in cold and warm periods in 2010 at an urban background site of Kozani, the major city and capital of the region which is located close to the power plants. Particulate matter concentration, particle-bound polycyclic aromatic hydrocarbons and anionic species concentrations were determined using gravimetric, GC-MS in SIM mode and Ion Chromatography analysis, respectively. For the cold period, the mean PM10 and PM2.5 mass concentration was found to be 19.62 and 14.68 µg m^?3, respectively. Correspondingly, for the warm period, the mean PM10 and PM2.5 values were 35.29 and 25.75 µg m^?3, respectively. In general, the results indicated that the major sources of air pollution in Kozani are traffic, combustion from agricultural activities and lignite power plants emissions, contributing by different percentages to each particle fraction.      

NMR and theoretical investigations on the structures and dynamics of octahedral bis(chelate)dichloro V(III) compounds isolated by an unusual reduction of non-oxo V(IV) species

Reaction of the non-oxo V(IV) species [V(IV)Cl(2)(L(OO))(2)] [L(OO) = acetylacetonate (acac(-)) or benzoylacetonate (bzac(-))] with a chelate nitrogen-donor ligand L(NN) in acetonitrile leads to the reduction of V(IV) to V(III) and the formation of the mononuclear V(III) compounds of the general formula [V(III)Cl(2)(L(OO))(L(NN))] (L(OO) and L(NN) are acac(-) and bipy for 1; acac- and 5,5'-me(2)bipy for 2; acac(-) and 4,4'-tb(2)bipy for 3; acac(-) and phen for 4; bzac(-) and bipy for 5; bzac(-) and phen for 6). The reduction of the V(IV) complexes was monitored by GC-MS and (1)H NMR spectroscopy. Both one- and two-dimensional (2D COSY and 2D EXSY) (1)H NMR techniques were used to assign the observed (1)H NMR resonances of 1-6 in CD(2)Cl(2) or CDCl(3) solution. It appeared that in solution these V(III) complexes form two isomers which are in equilibrium: cis-[V(III)Cl(2)(L(OO))(L(NN))] <==> trans-[V(III)Cl(2)(L(OO))(L(NN))]. 2D EXSY cross-peaks were clearly observed between bipy- and acac-hydrogen atoms of the two geometrical isomers of 1-3 as well as between bipy and acac(-) protons of the cis isomer, indicating a dynamic process that corresponds to cis-trans isomerization and a cis-cis racemization. The thermodynamic and kinetic parameters of the equilibrium between these two isomers were calculated for compounds 1 and 2 by using variable temperature (VT) NMR data. Both cis-trans isomerization and cis-cis racemization processes probably proceed with an intramolecular twist mechanism involving a trigonal prismatic transition state. Density functional calculations (DFT) also indicated such a rearrangement mechanism.     

Cyclization of 4,5‐Diamino Pyrazole Derivatives and Their Antibacterial Activities

A convenient synthesis of intermediate 4,5‐diamino‐3‐aryl‐1‐phenylpyrazoles 4a – 4c was reported. The different cyclization reactions were carried out with chalcone, 2‐mercaptoacetic acid and p‐anisialdehyde, ethyl chloroformate, glyoxal and thiourea to afford different N and S containing heterocycles. The reaction conditions were compared by conventional heating and microwave irradiation. The structures of the cyclization products were determined by analytical and spectroscopic data. All the synthesized compounds were screened for antibacterial activities in vitro.     

Synthesis of Polyfunctionally Substituted Fused Pyrimidine Derivatives as Antimicrobial Agents

A variety of pyrimidine derivatives 2—4 and annulated pyrimidine derivatives 5—17 have been synthesized via a sequence of heterocyclization reaction of readily available 6-naphthyl-4-oxo-2-thioxo-1,2,3,4-tetrahydroprimi-     

Studies of an Fe9 tridiminished icosahedron

The synthesis and structural characterization of a nonanuclear FeIII cage complex is reported. The nine iron centers in [Fe9(mu3-O)4(O3PPh)3(O2CCMe3)13] lie on the vertices of an incomplete icosahedron, with the P atoms of triphenylphosphonate at the other three vertices. The paramagnetic core therefore describes a tridiminished icosahedron. Magnetic studies suggest an S=1/2 ground state for the molecule. Analysis of exchange paths and the susceptibility data point to the interpretation that the cluster can be divided into two nearly decoupled sections: an {Fe6O3} section, with an S=0 ground state, in which three oxo-centered triangles bound a central triangle that is not oxo-centered; and an {Fe3O} triangle with S=1/2. The analysis of the susceptibility data leads to a Heisenberg model based on three significant antiferromagnetic exchange interactions, with values of 173.7 cm-1 in the {Fe3O} triangle, and 30.9 and 19.1 cm-1 within the {Fe6O3} section, while the exchange between them is <1 cm-1. With these assignments, the theoretical low-temperature differential susceptibility is also in very good agreement with measurements up to 50 T. Magnetic measurements in the milli-kelvin range reveal striking hysteresis loops and magnetization reversals associated with a Landau-Zener-Stückelberg (LZS) transition as enhanced by the occurrence of a phonon bottleneck.