Synthesis of 1,2,4-trioxepanes and 1,2,4-trioxocanes via photooxygenation of homoallylic alcohols

Homoallylic alcohols 4a-d, easily accessible in two steps from cyclopropyl methyl ketone, underwent a highly regioselective reaction with singlet oxygen to yield gamma-hydroxyhydroperoxides 5a-d in 57-72% yield. Acid-catalyzed reaction of 5a-d with acetone, cyclopentanone, and cyclohexanone furnished 1,2,4-trioxepanes 8a-d, 9a-d, and 10a-d in good yields. Homoallylic alcohol 12 also underwent a highly regioselective photooxygenation to yield gamma-hydroxyhydroperoxide 13 in 67% yield, which on reaction with acetone, cyclopentanone, and cyclohexanone, furnished 1,2,4-trioxocanes 16-18 in 41-55% yield.     

Monotone method for singular BVP in the presence of upper and lower solutions

In this paper we examine existence of monotone approximations of solutions of singular boundary value problem -(p(x)y^′(x))^′=q(x)f(x,y,py^′) for 0<x?b and lim_x→0⁺p(x)y^′(x)=0,α₁y(b)+β₁p(b)y^′(b)=γ₁. Under quite general conditions on f(x,y,py^′) we show that solution of the singular two point boundary value problem is unique. Here is allowed to have integrable singularity at x=0 and we do not assume .     

Determination of track registration efficiency and radiation chemical yield for loss of ester bonds due to gamma rays in Cellulose Acetate Butyrate (CAB) nuclear track detector

The fission track registration efficiency of an indigenously prepared Cellulose Acetate Butyrate (CAB) solid state nuclear track detector (SSNTD) has been determined and is found to be (0.89 ± 0.04). Radiation chemical yield, G-value for loss of ester bonds in this detector exposed to gamma rays from a Co-60 source has also been determined by FT-IR spectrometry. The amount of ester bonds lost due to the exposure was estimated from the change in absorbance of C=O and C–O–C bonds with the gamma dose. The G-value for breaking of ester bonds in CAB detector is found to be about 37/100 eV.     

Effect of the chain-length compatibility of surfactants and mechanical properties of mixed micelles on surfaces

Force/distance curves for silicon nitride tip/flat silica or alumina coated by a layer of mixed micelles of cationic/anionic surfactant are measured by using AFM. Mixtures of SDS/C(n)TAB (with molecular ratios of 3:1 and 20:1) and C(n)TAB/SDS (with molecular ratio of 85:15) were used for alumina and silica substrates, respectively. The number of carbon atoms per C(n)TAB molecule, n, was in the range of 8 to 16. On the basis of the force/distance curves, the elastic modulus, E, and yield strength, Y, of surface micelles are calculated. It is shown that in surfactant mixtures containing SDS the maximal repulsive force (the barrier F(bar)) at which the tip punctured the micelles, as well as the magnitudes of E and Y, attained the maximal values for C(12)TAB ( i.e., when the hydrocarbon chain lengths of two oppositely charged surfactants are the same). Obviously, it can be related to the highest density structure of these micelles. Note that the literature data for the surface micelles from pure C(n)TAB solutions demonstrate a monotonic dependence of F(bar), E, and Y on n in the range of n = 8-16, whereas the oppositely charged mixed surfactant systems yield much higher values of F(bar), E, and Y than does an equivalent chain length from the homologue series plots. The results obtained for mechanical characteristics of mixed micelles at the surface are compared with the results for the relaxation time, tau(2), that characterizes the lifetime (and therefore structure) of the bulk micelles. Both the dependence of F(bar), E, and Y on n for the surface mixed micelles and tau(2) on n for the bulk mixed micelles demonstrate a maximum at n = 12 for the C(n)TAB + SDS system. This correlation between properties of the surface and bulk micelles suggests that the mechanical properties of the surface micelles are largely determined by the interactions between surfactant molecules with surfactant-substrate interactions playing a secondary role.     

Lanthanum(III) and praseodymium(III) derivatives with dithiocarbamates derived from alpha-amino acids

Lanthanum(III) and praseodymium(III) complexes with dithiocarbamates have been synthesized by the reactions of lanthanum(III) and praseodymium(III) chloride with barium dithiocarbamate and complexes of type [LnCl(L)H2O]n have been obtained (where Ln=La(III) or Pr(III); L=barium salt of dithiocarbamate derived from glycine, L-leucine, L-valine, DL-alanine). The complexes have been characterized by elemental analysis, molar conductance, electronic absorption and fluorescence, infrared, far infrared, 1H NMR spectral studies. The presence of coordinated water molecule is inferred from thermogravimetric analysis which indicates the loss of one water molecule at 150-170 degrees C. The oscillator strength, Judd-Ofelt intensity parameter, stimulated emission cross-section, etc. have been obtained for different transitions of Pr3+.     

Quantitative determination of reserpine, ajmaline, and ajmalicine in Rauvolfia serpentina by reversed-phase high-performance liquid chromatography

A sensitive and reproducible reversed-phase high-performance liquid chromatography (HPLC) method using photodiode array detection is established for the simultaneous quantitation of important root alkaloids of Rauvolfia serpentina, namely, reserpine, ajmaline, and ajmalicine. A Chromolith Performance RP-18e column (100 x 4.6-mm i.d.) and a binary gradient mobile phase composed of 0.01 M (pH 3.5) phosphate buffer (NaH(2)PO(4)) containing 0.5% glacial acetic acid and acetonitrile are used. Analysis is run at a flow rate of 1.0 mL/min with the detector operated at a wavelength of 254 nm. The calibration curves are linear over a concentration range of 1-20 microg/mL (r = 1.000) for all the alkaloids. The various other aspects of analysis (i.e., peak purity, similarity, recovery, and repeatability) are also validated. For the three components, the recoveries are found to be 98.27%, 97.03%, and 98.38%, respectively. The limits of detection are 6, 4, and 8 microg/mL for ajmaline, ajmalicine, and reserpine, respectively, and the limits of quantitation are 19, 12, and 23 microg/mL for ajmaline, ajmalicine, and reserpine, respectively. The developed method is simple, reproducible, and easy to operate. It is useful for the evaluation of R. serpentina.     

3D QSAR studies on protein tyrosine phosphatase 1B inhibitors: comparison of the quality and predictivity among 3D QSAR models obtained from different conformer-based alignments

A set of 65 flexible peptidomimetic competitive inhibitors (52 in the training set and 13 in the test set) of protein tyrosine phosphatase 1B (PTP1B) has been used to compare the quality and predictive power of 3D quantitative structure-activity relationship (QSAR) comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) models for the three most commonly used conformer-based alignments, namely, cocrystallized conformer-based alignment (CCBA), docked conformer-based alignment (DCBA), and global minima energy conformer-based alignment (GMCBA). These three conformers of 5-[(2S)-2-({(2S)-2-[(tert-butoxycarbonyl)amino]-3-phenylpropanoyl}amino)3-oxo-3-pentylamino)propyl]-2-(carboxymethoxy)benzoic acid (compound number 66) were obtained from the X-ray structure of its cocrystallized complex with PTP1B (PDB ID: 1JF7), its docking studies, and its global minima by simulated annealing. Among the 3D QSAR models developed using the above three alignments, the CCBA provided the optimal predictive CoMFA model for the training set with cross-validated r2 (q2)=0.708, non-cross-validated r2=0.902, standard error of estimate (s)=0.165, and F=202.553 and the optimal CoMSIA model with q2=0.440, r2=0.799, s=0.192, and F=117.782. These models also showed the best test set prediction for the 13 compounds with predictive r2 values of 0.706 and 0.683, respectively. Though the QSAR models derived using the other two alignments also produced statistically acceptable models in the order DCBA>GMCBA in terms of the values of q2, r2, and predictive r2, they were inferior to the corresponding models derived using CCBA. Thus, the order of preference for the alignment selection for 3D QSAR model development may be CCBA>DCBA>GMCBA, and the information obtained from the CoMFA and CoMSIA contour maps may be useful in designing specific PTP1B inhibitors.     

First principles study of neutral and anionic (medium-size) aluminum nitride clusters: AlnNn, n=7-16

We report the results of a theoretical study of AlnNn (n=7-16) clusters that is based on density functional theory. We will focus on the evolution of structural and electronic properties with the cluster size in the stoichiometric AlN clusters considered. The results reveal that the structural and electronic properties tend to evolve toward their respective bulk limits. The rate of evolution is, however, slow due to the hollow globular shape exhibited by the clusters, which introduces large surface effects that dominate the properties studied. We will also discuss the changes induced upon addition of an extra electron to the respective neutral clusters.     

Reaction of Triethyl Phosphonoacetate Anion with Phenylhydrazones: A New Method for the Preparation of 3(2H)-Pyridazinones

Various 5,6-disubstituted-2-phenyl-3(2H)-pyridazinones 4 have been synthesised by reacting triethyl phosphonoacetate anion with monophenylhydrazone of 1,2-dicarbonyl compounds 2.     

Approximate analytical solution of two-dimensional space-time fractional diffusion equation

This work presents an iterative scheme for the numerical solution of the space-time fractional two-dimensional advection–reaction–diffusion equation applying homotopy perturbation with Laplace transform using Caputo fractional-order derivatives. The solution obtained is beneficial and significant to analyze the modeling of superdiffusive systems and subdiffusive system, anomalous diffusion, transport process in porous media. This iterative technique presents the combination of homotopy perturbation technique, and Laplace transforms with He's polynomials, which can further be applied to numerous linear/nonlinear two-dimensional fractional models to computes the approximate analytical solution. In the present method, the nonlinearity can be tackle by He's polynomials. The salient features of the present scientific work are the pictorial presentations of the approximate numerical solution of the two-dimensional fractional advection–reaction–diffusion equation for different particular cases of fractional order and showcasing of the damping effect of reaction terms on the nature of probability density function of the considered two-dimensional nonlinear mathematical models for various situations.