Copper-promoted carbon-nitrogen bond formation with 2-iodo-selenophene and amides

We present here carbon-nitrogen bond formation via a coupling reaction of 2-iodo-selenophene catalyzed by Cu(I) in the presence of a base and an inexpensive ligand, and establish the first route to obtaining 2-nitrogen-selenophene derivatives in good yields. We can anticipate that this reaction works well with oxazolidinones, lactams, and aliphatic and aromatic amides, as nitrogen sources, in the absence of any supplementary additives. In addition, the reaction proceeded cleanly under mild reaction conditions and was sensitive to the ratio of amide/2-iodo-selenophene, as well as the nature of the ligand, base, and solvent.     

Adsorptive micro-extraction techniques--novel analytical tools for trace levels of polar solutes in aqueous media

A novel enrichment technique, adsorptive μ-extraction (AμE), is proposed for trace analysis of polar solutes in aqueous media. The preparation, stability tests and development of the analytical devices using two geometrical configurations, i.e. bar adsorptive μ-extraction (BAμE) and multi-spheres adsorptive μ-extraction (MSAμE) is fully discussed. From the several sorbent materials tested, activated carbons and polystyrene divinylbenzene phases demonstrated the best stability, robustness and to be the most suitable for analytical purposes. The application of both BAμE and MSAμE devices proved remarkable performance for the determination of trace levels of polar solutes and metabolites (e.g. pesticides, disinfection by-products, drugs of abuse and pharmaceuticals) in water matrices and biological fluids. By comparing AμE techniques with stir bar sorptive extraction based on polydimethylsiloxane phase, great effectiveness is attained overcoming the limitations of the latter enrichment approach regarding the more polar solutes. Furthermore, convenient sensitivity and selectivity is reached through AμE techniques, since the great advantage of this new analytical technology is the possibility to choose the most suitable sorbent to each particular type of application. The enrichment techniques proposed are cost-effective, easy to prepare and work-up, demonstrating robustness and to be a remarkable analytical tool for trace analysis of priority solutes in areas of recognized importance such as environment, forensic and other related life sciences.     

Neumann Boundary Conditions Inhibiting SSB in Coleman-Weinberg Mechanism

In this work we show that homogeneous Neumann boundary conditions inhibit the Coleman-Weinberg mechanism for spontaneous symmetry breaking in the scalar electrodynamics if the length of the finite region is small enough （a = e2Mφ-1, where M, is the mass of the scalar field generated by the Coleman-Weinberg mechanism）.     

Determination of ytterbium in animal faeces by tungsten coil electrothermal atomic absorption spectrometry

A method for ytterbium determination in animal faeces by tungsten coil electrothermal atomic absorption spectrometry (TCAAS) was developed. Faeces were dry-ashed in a muffle furnace, the ashes were treated with hydrochloric acid, and 10 mul of sample solution were delivered into 150-W tungsten coil atomizer. A matrix-matching procedure employing a 66-s heating program proved to be efficient for obtaining accurate results. Characteristic mass and detection limit were 7.1 pg and 0.35 mug g(-1) Yb, respectively. The tungsten coil atomizer lifetime exceeded 300 firings with digested solutions and R.S.D. of measurements was 1.9% after ten consecutive injections of 10.0 mug l(-1) Yb. Accuracy of the proposed method was assessed by employing a graphite furnace atomic absorption spectrometric procedure. Application of the paired t-test did not reveal any significant difference for ytterbium contents determined by both methods at 95% confidence level. It was demonstrated that the proposed procedure can successfully be used for evaluation of kinetic passage rate of feed through digestive tract of animals.     

Formation of negative ions by electron impact on SiF4 and CF4

First measurements of cross sections for the formation of negative ions by electron attachment to SiF₄ and CF₄ are reported for an electron impact energy range of 0 to 50 eV. The energies at which the various ions appear and the positions at which the ionization efficiency curves peak have been obtained and compared with previous measurements. Thermochemical data have been used to predict and identify the various channels of dissociation. Cross sections for the production of ion pairs through the process of polar dissociation have also been measured.Visiting fellow, on leave of absence from Universidade Federal de Sao Carlos, Departamento de Quimica, 13560, Sao Carlos, SP, Brazil     

SERRS study of [Ru(CN)<Subscript>5</Subscript>(pyS)]<Superscript>4−</Superscript> SAM and cytochrome c: A suggestion toward the heterogeneous molecular recognition

Surface-Enhanced Raman Scattering (SERS) spectra of [Ru(CN)₅(pyS)]⁴⁻ (RupyS) complex self-assembled monolayer (SAM) were obtained on gold and silver surfaces at 632.8 and 413.1 nm excitation radiations, respectively. The bands assigned to the heme iron of the cytochrome c (cyt c) metalloprotein group were observed by using the RupyS SAM on silver at 413.1 nm. The Surface-Enhanced Resonance Raman Scattering (SERRS) spectra of the RupyS SAM on silver in the cyt c solution obtained at −0.2 and +0.2 V present bands at 1,365 and 1,374 cm⁻¹ characteristic of the heme group, indicating the reduced and oxidized states of this protein, respectively. The bands observed at 1,464, 1,504, and 1,638 cm⁻¹ are used to confirm the redox state of cyt c. The presence of the oxidized and reduced bands in function of different applied potential is an evidence that the protein is interacting with the modifier. This paper is dedicated to Prof. Francisco Nart, in memoriam.     

Thermal behavior of copper(II) pseudohalide complexes containing bidentate amines

Pseudohalide complexes of copper(II) with aliphatic bidentate amines, [Cu(N₃)₂(N,N-diEten)]₂ 1, [Cu(NCO)₂(N,N-diEten)]₂ 2, [Cu(NCO)₂(N,N-diMeen)]₂ 3, [Cu(N₃)(NCS)(N,N'-diMeen)]₂ 4 and [Cu(N₃)(NCO)(N,N-diMeen)]₂ 5 (N,N-diEten=N,N-diethylethylenediamine; N,N-diMeen=N,N- dimethyl-ethylenediamine and N,N'-diMeen = N,N'-dimethylethylenediamine), were prepared, characterized and their thermal behavior was investigated by TG curves. According to thermal analysis and X-ray diffraction patterns all compounds decomposed giving copper(II) oxide as final product. The mechanisms of decomposition were proposed and an order of thermal stability was established.This revised version was published online in November 2005 with corrections to the Cover Date.     

Study of layered and defective amorphous solids by means of thermal wave method

In this work the thermal properties and the thickness calibration in layered thick acrylic films using the thermal wave method are reported. The results from acrylic films on two different substrates showed that thermal diffusivity and conductivity can be measured for both supports, metallic and glassy. The experimental applicability of a 1-D model and accuracy of the thickness measurement are also discussed.     

Matrix Solid-Phase Dispersion Extraction for Analysis of Cypermethrin Residue in Cows’ Milk

A method of extraction based on matrix solid-phase dispersion has been developed, optimized, and validated by chromatographic analysis of cypermethrin pesticide residues in samples of cows’ milk. Milk (0.25 g) was fortified with cypermethrin and blended with 1 g each of C₁₈ (octadecylsilane) silica and Na₂SO₄ (anhydrous sodium sulfate), used to trap fats and water, respectively. The homogenized material was transferred to a commercial SPE cartridge containing 1 g activated Florisil with 5 mL acetonitrile. Cypermethrin was eluted under vacuum with 5 × 2 mL acetonitrile and the extract was concentrated to 1 mL and analyzed by gas chromatography–mass spectrometry. The limits of detection and quantification of the method were 0.025 and 0.08 mg kg⁻¹, respectively.