Extractive spectrophotometric determination of Cobalt(II) in synthetic and pharmaceutical samples using Cyanex 923.

Cyanex 923 has been proposed as a sensitive analytical reagent for the direct extractive spectrophotometric determination of cobalt(II). Cobalt(II) forms a blue-colored complex with Cyanex 923 in the organic phase. The maximum absorbance of the complex is measured at 635 nm. Beer's law was obeyed in the range 58.9 - 589.0 microg of cobalt. The molar absorptivitiy and Sandell's sensitivity of the complex was calculated to be 6.79 x 10920 l mol(-1) cm(-1) and 0.088 microg cm(-2), respectively. The nature of the extracted species was found to be Co(SCN)2 x 2S. An excellent linearity with a correlation coefficient value of 0.999 was obtained for the Co(II)-Cyanex 923 complex. Stability and regeneration of the reagent (Cyanex 923) for reuse is the main advantage of the present method. The method was successfully applied to the determination of cobalt in synthetic mixtures and pharmaceutical samples was found to give values close to the actual ones. Standard alloy samples, such as high-speed tool BCS 484 and 485, have been tested for the determination of cobalt for the purpose of validating the present method. The results of the proposed method are comparable with atomic absorption spectrometry and were found to be in good agreement.     

A simple TiCl4 promoted arylation of orthoformate and benzyl ethers by N,N-dialkylarylamines

N,N-Dialkylarylamines react with trimethyl orthoformate and TiCl₄ under ambient conditions to give the corresponding formyl derivatives in 75-89% yields, whereas the corresponding arylated products are obtained from benzyl ethers and acetals in 42-78% yields.     

51V solid-state magic angle spinning NMR spectroscopy and DFT studies of oxovanadium(V) complexes mimicking the active site of vanadium haloperoxidases

A series of 11 oxovanadium(V) complexes mimicking the active site of vanadium haloperoxidases have been investigated by (51)V magic angle spinning NMR spectroscopy and density functional theory (DFT). The MAS spectra are dominated by the anisotropic quadrupolar and chemical shielding interactions; for these compounds, C(Q) ranges from 3 to 8 MHz, and delta(sigma) is in the range 340-730 ppm. The quadrupolar coupling and chemical shielding tensors as well as their relative orientations have been determined by numerical simulations of the spectra. The spectroscopic NMR observables appear to be very sensitive to the details of the electronic and geometric environment of the vanadium center in these complexes. For the four crystallographically characterized compounds from the series, the quadrupolar and chemical shielding anisotropies were computed at the DFT level using two different basis sets, and the calculated tensors were in general agreement with the experimental solid-state NMR data. A combination of (51)V solid-state NMR and computational methods is thus beneficial for investigation of the electrostatic and geometric environment in diamagnetic vanadium systems with moderate quadrupolar anisotropies.     

Modified silver staining in 2DE improves protein detection even at extremely low sample concentration

The typical concentration of protein loaded varies from 0.13 to 1.40 μg/μL for a classical silver staining method in 2DE gel. Here, we present a simple modified classical silver staining method by modifying the silver impregnation and development reaction steps. This modified method detects the protein spots at extremely low loaded concentrations, ranging from 0.0048 to 0.0480 μg/μL. We recommend this modified silver staining as an excellent method for the limited biological samples used for silver‐stained 2DE analysis. Altogether, the protocol takes close to two days from first dimension separation to second dimension separation, followed by silver staining, scanning, and analysis.     

Mortar element methods for parabolic problems

In this article a standard mortar finite element method and a mortar element method with Lagrange multiplier are used for spatial discretization of a class of parabolic initial‐boundary value problems. Optimal error estimates in L^∞(L²) and L^∞(H¹)‐norms for semidiscrete methods for both the cases are established. The key feature that we have adopted here is to introduce a modified elliptic projection. In the standard mortar element method, a completely discrete scheme using backward Euler scheme is discussed and optimal error estimates are derived. The results of numerical experiments support the theoretical results obtained in this article. © 2008 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 2008     

Propagation of plane waves in microstretch fluid

The propagation of plane harmonic waves are studied in a microstretch fluid medium. It is found that five basic waves can propagate at distinct speeds in an infinite linear homogeneous isotropic microstretch fluid. Out of these five waves, one is a longitudinal micro-rotational wave, two are coupled longitudinal waves and remaining two are coupled transverse waves. The longitudinal micro-rotational wave travels independently and is not influenced by the microstretching of the medium, while the coupled longitudinal waves arise due to the presence of microstretching and coupled transverse waves arise due to the presence of micro-rotation in the medium. Speed of propagation of all the waves are found to be complex valued and dispersive at low frequency, but almost non-dispersive at high frequency. Due to complex valued speeds of propagation, all the waves are attenuating but differently. Coupled sets of longitudinal waves reduce to a longitudinal wave of micropolar fluid in the absence of microstretching. Reflection phenomena of a set of coupled longitudinal waves incident obliquely at the free surface of a microstretch fluid half-space has been investigated. Closed formulae for the reflection coefficients are presented and computed numerically for a particular medium. The real and imaginary parts of the complex speeds of all the waves and their corresponding attenuation coefficients have also been studied numerically and depicted graphically against frequency parameter.     

A theoretical study on structural, spectroscopic and energetic properties of acetamide clusters [CH3CONH2] (n=1-15)

Insights into the formation of hydrogen bonded clusters are of outstanding importance and quantum chemical calculations play a pivotal role in achieving this understanding. Structure and energetic comparison of linear, circular and standard forms of (acetamide)(n) clusters (n = 1-15) at the B3LYP/D95** level of theory including empirical dispersion correction reveals significant cooperativity of hydrogen bonding and size dependent structural preference. A substantial amount of impact of BSSE is observed in these calculations as the cluster size increases irrespective of the kind of arrangement. The interaction energy per monomer increases from dimer to 15mer by 90% in the case of the circular arrangement, by 76% in the case of the linear arrangement and by 34% in the case of the standard arrangement respectively. The cooperativity in hydrogen bonding is also manifested by a regular decrease in average OH and C-N bond distances, while average C=O and N-H bond lengths increase with increasing cluster size. Atoms-In-Molecules (AIM) analysis is used to characterize the nature of hydrogen bonding between the acetamide molecules in the cluster on the basis of electron density (ρ) values obtained at the bond critical point. An analysis of N-H bond stretching frequencies as a function of the cluster size shows a marked red shift as the cluster size increases from 1 to 15.     

Structures and energetics of darunavir and active site amino acids of native and mutant HIV–1 protease: a computational study

Structural Chemistry - Quantum chemical calculations have been performed at the M06–2X/6–31G(d,p) level of theory to investigate the strength and nature of interactions between the...