Mono Halogenation of β-Keto Sulfides. Synthesis of β-Keto-α-phenylthio p-Tolyl Sulfones

β-Keto-α-Phenylthio p-Tolyl sulfones are obtained from β-keto-alkyl phenyl sulfides by halogenation with NCS followed by treatment with sodium p-toluene sulphinate.     

Nitroprusside-PEO enthalpic interaction as a driving force for partitioning of the [Fe(CN)(5)NO](2-) anion in aqueous two-phase systems formed by poly(ethylene oxide) and sulfate salts

Ions are known to concentrate in the salt-enriched phase of aqueous two-phase systems, with the only known exception being the pertechnetate anion, TcO(4)(-). We have discovered a second ion, nitroprusside anion (NP), which is markedly transferred from the salt phase to the polymer phase. The partitioning behavior of [Fe(CN)(5)NO](2-) anion was investigated in ATPS formed by poly(ethylene oxide) of molar mass 3350 and 35000 g mol(-1), and different sulfate salts (Na(2)SO(4), Li(2)SO(4), and MgSO(4)). On the basis of a model, the nitroprusside high affinity for the macromolecular phase was attributed to an enthalpic specific interaction between the anion and ethylene oxide unit. Partition coefficients increased exponentially with tie-line length increase, reaching values as high as 1000 and showing a relationship very dependent on the salt nature, but independent of the polymer molar mass.     

Ion plated indium oxide : infrared and optical study

The high optical transparency of ion plated indium oxide combined with their mechanical hardness and good environmental stability have opened up numerous applications in the line of sophisticated optoelectronic devices. Indium is evaporated at a low oxygen pressure on to an ordinary glass substrate mounted under the cathode and biased by a r.f. generator at 13,6 M Hz. Infrared spectra are recorded in the range 5000–200 cm^?1 by A.T.R. and reflexion-absorption spectroscopy, and show between 800 and 200 cm^?1 bands due to stretching and bending modes predicted by a factor group analysis. A tentative assignment is made of the highest frequency. Last U.V. and visible spectra are discussed.     

On the low-lying excited states of sym-triazine-based herbicides.

We report a joint computational and luminescence study on the low-lying excited states of sym-triazines, namely, 1,3,5-triazine (1) and the ubiquitous herbicides atrazine [6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine (2)] and ametryn [6-methylthio-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine (3)]. Geometrical structures, energetics, and transition and state properties of I and 2 were computed at the TD-DFT, CASSCF, and CASPT2 levels of theory. The fluorescence and phosphorescence emission spectra, lifetimes, and fluorescence quantum yields were measured for the three compounds, and from these, the energies of the lowest excited states and their corresponding radiative rates were determined. The predictions from CASPT2 calculations are in good agreement with the experimental results obtained from the luminescence studies and allow the interpretation of different absorption and emission features.     

Static charged spheres with anisotropic pressure in general relativity

We report a generalization of our earlier formalism [Pramana, 54, 663 (1998)] to obtain exact solutions of Einstein-Maxwell’s equations for static spheres filled with a charged fluid having anisotropic pressure and of null conductivity. Defining new variables: w=(4π/3)(ρ+ε)r ², u=4πξr ², v _r=4πp _r r ², v _⊥=4πp _⊥ r ²[ρ, ξ(=−(1/2)F ₁₄ F ¹⁴), p _r, p _⊥ being respectively the energy densities of matter and electrostatic fields, radial and transverse fluid pressures whereas ε denotes the eigenvalue of the conformal Weyl tensor and interpreted as the energy density of the free gravitational field], we have recast Einstein’s field equations into a form easy to integrate. Since the system is underdetermined we make the following assumptions to solve the field equations (i) u=v _r=(a ²/2κ)r ⁿ⁺², v _⊥=k ₁ v _r, w=k ₂ v _r; a ², n(>0), k ₁, k ₂ being constants with κ=((k ₁+2)/3+k ₂) and (ii) w+u=(b ²/2)r ⁿ⁺², u=v _r, v _⊥−v _r=k, with b and k as constants. In both cases the field equations are integrated completely. The first solution is regular in the metric as well as physical variables for all values of n>0. Even though the second solution contains terms like k/r ² since Q(0)=0 it is argued that the pressure anisotropy, caused by the electric flux near the centre, can be made to vanish reducing it to the generalized Cooperstock-de la Cruz solution given in [14]. The interior solutions are shown to match with the exterior Reissner-Nordstrom solution over a fixed boundary. Dedicated to Prof. F A E Pirani.     

A short range many-body potential for modelling bcc metals

The problem considered is the fitting of a many-body interaction potential to bulk crystal data. A parameterisation of the potential is assumed which is based on physical considerations. The free parameters are determined by using global optimization to perform a least squares fit, to a large number of crystal properties. This has been achieved for body centered cubic (bcc) materials. The approach adopted here fits the bcc crystal structure, as the preferred minimum energy configuration for tungsten, and also fits the dimer energetics and the elastic properties of crystalline tungsten.     

Alcaloides steroidiques—LII Alcaloides du buxus balearica Willd.: Cycloprotobuxine-D, buxamine-E, buxaminol-E, N-isobutyryl-baleabuxidine-F, N-benzoyl-baleabuxidine-F, baleabuxoxazine-C, N-isobutyryl-baleabuxidienine-F, N-benzoyl-baleabuxidienine-F, N-isobutyryl-baleabuxaline-F

The following alkaloides have been extracted from the leaves of Buxus balearica Willd.: cyclomicrophylline-B, cycloprotobuxines A, C and D, baleabuxine (N-isobutyryl-baleabuxine-F), buxamine-E and buxaminol-E (already reported), N-isobutyryl- and N-benzoyl-baleabuxidine-F, baleabuxoxazine-C, N-isobutyryl- and N-benzoyl-baleabuxidienine-F, N-isobutyryl-baleabuxaline-F, the structures of which are proposed. The stereochemistry of baleabuxidines and baleabuxoxazines is established on the base of chemical correlations between these two groups and cyclomicrophyllines.     

Headspace-solid phase microextraction-gas chromatography as a tool to define an index that establishes the retention capacity of the wine polymeric fraction towards ethyl esters

A headspace-solid phase microextraction followed by gas chromatographic analysis (HS-SPME-GC) was developed to be applied in the study of the interactions between the wine polymeric fraction and the ethyl esters: ethyl hexanoate, ethyl octanoate, and ethyl decanoate. Wine models (WM) were prepared with 10% (v/v) aqueous ethanol at pH 3.5 with distinct wine polymeric concentrations prepared from white wine of Vitis vinifera L. var. Fern?o-Pires: 1.0 g L(-1) (PWM1), with a polymeric concentration approaching the real one in wine; 10.0 g L(-1) (PWM10); and 30.0 g L(-1) (PWM30), saturated with polymeric fraction. A reference wine model (RWM) was prepared without polymeric fraction. Each volatile compound (4.0 mg L(-1)) was added separately to the RWM and to the WM with the three levels of polymeric material (PWM). From the retention index (RI) calculated for each compound using the formula: [RI = 1 - (C(RWM) - C(PWM))/C(RWM)], where C(RWM) is the concentration of the compound in the RWM and C(PWM) is the concentration of the compound in the given PWM, the retention capacity of each wine polymeric fraction towards the three esters was established. The higher retention indexes were observed for ethyl decanoate, the more hydrophobic compound, and for the PWM with higher concentration. Furthermore, this study also suggested that the retained compounds are dosed to the headspace, which may promote the perception of their aroma for a longer period of time.