Defect-molecule parameters for the divacancy in silicon

The hamiltonian eigenvalue problem is solved for a diva cancy in silicon within the framework of the defect-molecule model. A direct connection between the solution of this problem and a self-consistent multiple-scattering cluster calculation is established in order to determine the parameters of the model. The obtained results provide a quantitative confirmation of the currently accepted microscopic picture of the divacancy.     

Effects of X-ray absorption in the analysis of thick target samples by XRF

The accuracy of the quantitative analysis of thick targets by XRF is impaired by effects due to the absorption of X-rays in the matrix associated with the non-uniformity of the X-ray beam and the lack of knowledge of the actual distribution of trace elements in the target. The uncertainty in the elemental mass associated to a definite number X-rays detected is discussed in the paper. A correction factor is derived to account specifically for the effect of the absorption of X-rays and the non-uniformity of the X-ray beam. Work partially supported by Conselho Nacional de Desenvolvimento Científico e Tecnológico, Financiadora de Estudos e Projetos and International Atomic Energy Agency.     

Correction to: Plasma processed carbon thin films applied to dye-sensitized solar cells

Journal of Solid State Electrochemistry - The authors regret an error in the Experimental section of the published article:     

Michael additions of primary and secondary amines to acrylonitrile catalyzed by lipases

The present Letter details our findings on the lipase-catalyzed Michael reactions between primary or secondary amines and acrylonitrile. Several lipases were evaluated, and good results were obtained leading to the formation of Michael adducts in shorter reaction times than the uncatalyzed reactions.     

Effect of TiO<Subscript>2</Subscript> surface modification in Rhodamine B photodegradation

Commercial TiO₂ nanoparticles were superficially modified through polymeric resins obtained from polymerization of citrate complexes of Y³⁺ and Al³⁺ with ethylenglycol. The materials were treated at 450 °C for 4 h to obtain modified nanoparticles, which were characterized by HR-TEM, Zeta potential and surface area through N₂ fisisorption. Rhodamine B photodegradation by visible light irradiation and in presence of those modified nanoparticles was compared with the same process in presence of unmodified commercial TiO₂ nanoparticles. It was observed, by UV–visible spectroscopy, that the catalytic photoactivity in presence of modified nanoparticles was smaller than that observed with commercial TiO₂ nanoparticles. However, the surface modifier played an important role in the photodegradation kinetic process, showing a non-linear relation between modifier amount and photodegradation rate, presenting a maximum value at 0.8% (w/w).     

ESI-TEM imaging of surfactants and ions sorbed in Stöber silica nanoparticles

The sorption of surfactants and NaCl in silica nanosized particles creates unexpected spatial distributions of solutes that were evidenced by electron spectroscopy imaging in the transmission electron microscope (ESI/TEM). The spectral images show that simple ions (Na(+), Cl(-), Br(-)) are actually absorbed within the particles irrespective of their charges, while surfactant chains are adsorbed at the particle surfaces. The expected effect of the surfactants on particle aggregation is also observed in the micrographs. In the case of salt, close-packed silica particle arrays are formed at low ionic strength, but only coarse aggregates form at higher salt concentrations. The particles absorb both Na(+) and Cl(-) ions in similar amounts, from 0.5 mol L(-)(1) NaCl, but Na(+) ions are depleted from the particles' immediate outer vicinity, where Cl(-) ions are in turn accumulated. These results confirm that St?ber silica nanoparticles are highly porous and reveal their potential usefulness as carriers of small molecules and ions, due to the small particle size, exceptional colloidal stability, and this newly found sorption behavior.     

Syntheses, structural and spectroscopic characterization of novel zinc(II)-bis(trithiocarbimato) complexes and bis(N-methylsulfonyldithiocarbimate)-sulfide

Four zinc(II)-bis(trithiocarbimato) complexes with the general formula A₂[Zn(RSO₂NCS₃)₂] [A = Ph₄P⁺: R = CH₃ (1), 4-CH₃C₆H₄ (2); A = Bu₄N⁺: R = CH₃ (3), 4-CH₃C₆H₄ (4)] were obtained by the reaction of sulfur with the correspondent zinc(II)-bis(dithiocarbimato) complexes. Additionally, the compound (Ph₄P)₂[(CH₃SO₂NCS₂)₂S)] (5) was prepared from the potassium methylsulfonildithiocarbimate by oxidation with iodine. The compounds were characterized by elemental analyses and IR, ¹H NMR and ¹³C NMR spectroscopies. The compounds 4 and 5 were also characterized by X-ray diffraction techniques. The compound 4 crystallizes in the centrosymmetric space group C2/c of the monoclinic system. The Zn(II) is in a distorted tetrahedral environment (ZnS₄) in compound 4, and differ from the coordination mode observed in compound 1, which involves one sulfur and one nitrogen atom of each trithiocarbimate ligand. Compound 5 is the first example of a compound containing a bis(N-alkylsulfonyldithiocarbimate)-sulfide dianion and crystallises in the non-centrosymmetric space group P4₁2₁2 of the tetragonal system.     

Comparative computational studies of 3,4-dihydro-2,6-diaryl-4-oxo-pyrimidine-5-carbonitrile derivatives as potential antinociceptive agents

In this study, the antinociceptive properties of 3,4-dihydro-2,6-diaryl-4-oxo-pyrimidine-5-carbonitrile derivatives 5a-i at doses of 25 and 50 mg/kg were evaluated in mice, using the abdominal constriction test. Molecular modeling studies were also performed using density functional theory calculations. These data provided information about the electrostatic and ionization potentials and were used to compare the antinociceptive activity of the title compounds. The most active compounds were 3,4-dihydro-2-(4-chlorophenyl)-6-(4-methoxyphenyl)-4-oxo-pyrimidine-5-carbonitrile (5b) and 3,4-dihydro-2,6-diphenyl-4-oxo-pyrimidine-5-carbonitrile (5i), which inhibited the number of abdominal constrictions, at 50 mg/kg dose, in 88.6% and 88% of the sample, respectively. A preliminary SAR study demonstrated that halogen replacement in the phenyl rings of the compounds under study reduces the antinociceptive activity. DFT calculations showed that there is a high correlation between the ionization potentials and the analgesic properties of the compounds. It was found that compounds with a positive ionization potential (compounds 5b and 5i) were found to be the best analgesic drugs in this series.     

Quantum-chemical Modeling of the Reaction of 3-Pyridinecarbaldehyde with 3-Cyano-4,5,5-trimethyl-2(5H)-furanone

The condensation of pyridinecarbaldehydes with 3-cyano-4,5,5-trimethyl-2(5H)-furanone and 3-cyano-4,6,6-trimethyl-5,6-dihydro-2(2H)-pyranone leads to the formation of the products of crotonic condensation and compounds of the Michael adduct type. A model investigation of the mechanism by the semiempirical AM1 quantum-chemical method for the case of the reaction of 3-pyridinecarbaldehyde with 3-cyano-4,5,5-trimethyl-2(5H)-furanone showed that the products can be formed in parallel from one and the same intermediate compound.