Accelerated Bergman cyclization of porphyrinic-enediynes

The Bergman cyclization of simple diethynylporphyrinic-enediynes exhibits a double activation barrier to the formation of Bergman cyclized product. Addition of H-atom acceptor accelerates the formation of the picenoporphyrin, indicating that the second barrier is rate limiting.     

Steady-state self-focusing of Gaussian electromagnetic beams in an inhomogeneous nonlinear medium: Effect of absorption and initial curvature of the beam

The authors have investigated the effect of linear absorption and initial curvature of an electromagnetic Gaussian beam on focusing/defocusing in an inhomogeneous nonlinear medium. Numerical computations have been made for linear inhomogeneity and saturating nonlinearity, characteristic of dielectrics and collisional plasmas. The maximum and minimum of the beam width keep decreasing with increase in distance of propagation (or absorption), till the beam becomes very weak and diverges steeply; penetration in an overdense medium also decreases with increasing absorption. Converging beams initially converge and then go in: (i) the oscillatory divergence (ii) self-focusing or (iii) steady divergence mode, depending upon the initial values of beam width and axial irradiance. The maximum penetration in an overdense medium has the highest values for −0.7<(df/dξ)_ξ=0<0.4 and falls sharply, outside these limits.     

Artabotryols A – E,New Lanostane Triterpenes from the Seeds of Artabotrys odoratissimus

Six new lanostane triterpenes, artabotryols A, B, C1, C2, D, and E ( 1, 2, 3a, 3b, 4 , and 5 , resp.) have been isolated from the seeds of Artabotrys odoratissimus (Annonaceae). Their structures have been established as (3α,22S,25R)‐3‐hydroxy‐22,26‐epoxylanost‐8‐en‐26‐one ( 1 ), (3α,22S,25R)‐22,26‐epoxylanost‐8‐ene‐3,26‐diol ( 2 ), (3α,22S,25R,26R)‐26‐methoxy‐22,26‐epoxylanost‐8‐en‐3‐ol ( 3a ), (3α,22S,25R, 26S)‐26‐methoxy‐22,26‐epoxylanost‐8‐en‐3‐ol ( 3b ), (3α,22S,25R)‐3,22‐dihydroxylanost‐8‐en‐26‐oic acid ( 4 ) and (3α,7α,11α,22S,25R)‐3,7,11‐trihydroxy‐22,26‐epoxylanost‐8‐en‐26‐one ( 5 ) by spectroscopic studies and chemical correlations.     

Synthesis and characterization of complexes imparting N-pyridyl bonded meso-pyridyl substituted dipyrromethanes

The meso-pyridyl substituted dipyrromethane ligands 5-(4-pyridyl)dipyrromethane (4-dpmane) and 5-(3-pyridyl)dipyrromethane (3-dpmane) have been employed in the synthesis of a series of complexes with the general formulations [(η⁶-arene)RuCl₂(L)] (η⁶-arene = C₆H₆, C₁₀H₁₄) and [(η⁵-C₅Me₅)MCl₂(L)] (M = Rh, Ir). The reaction products have been characterized by microanalyses and spectral studies and molecular structures of the complexes [(η⁶-C₁₀H₁₄)RuCl₂(4-dpmane)] and [(η⁵-C₅Me₅)IrCl₂(3-dpmane)] have been determined crystallographically. For comparative studies, geometrical optimization have been performed on the complex [(η⁵-C₅Me₅)IrCl₂(4-dpmane)] using exchange correlation functional B3LYP. Optimized bond length and angles are in good agreement with the structural data of the complex [(η⁵-C₅Me₅)IrCl₂(3-dpmane)]. The complexes [(η⁶-C₁₀H₁₄)RuCl₂(3-dpmane)], [(η⁵-C₅Me₅)RhCl₂(3-dpmane)] and [(η⁵-C₅Me₅)IrCl₂(3-dpmane)] have been employed as a transfer hydrogenation catalyst in the reduction of aldehydes. It was observed that the rhodium and iridium complexes mentioned above are more effective in this regard in comparison to the ruthenium complex.     

Quantitative evaluation of benzene, toluene, and xylene in the larvae of Drosophila melanogaster by solid-phase microextraction/gas chromatography/mass spectrometry for potential use in toxicological studies

A simple, rapid, and solvent-free method for quantitative determination of benzene, toluene, and Xylene in exposed Drosophila larvae was developed using headspace solid-phase microextraction (HS-SPME) coupled to GC/MS. Larvae fed on standard Drosophila food mixed with benzene, toluene, and Xylene for 48 h were homogenized in Milli-Q water. Extraction of benzene, toluene, and Xylene was performed at 65 degrees C for 30 min on the SPME fiber (silica-fused). Subsequently, the fiber was desorbed in the GC injection port, followed by GC/MS analysis in the selected-ion monitoring mode. An external calibration curve was used for the quantification of benzene, toluene, and Xylene in the exposed organism. Recoveries were in the range of 78-82% (intraday) and 76-81% (interday) in larvae, and 91-96% (intraday) and 87-92% (interday) in the diet. LOD with an S/N of 3:1 and LOQ with an S/N of 10:1 were in the range of 0.01-0.023 and 0.034-0.077 microg/L, respectively. Percent RSD values for benzene, toluene, and Xylene were in the range of 0.50-0.81 (intraday) and 0.89-1.23 (interday) for retention time, and 2.16--3.85 (intraday) and 2.99-4.95 (interday) for peak concentration, showing good repeatability. This method was sensitive enough to quantitate benzene, toluene, and Xylene in small exposed organisms like Drosophila larvae. The SPME/GC/MS method developed may have wider applications in various in vivo toxicological studies.     

Base catalyzed multicomponent synthesis of spiroheterocycles with fused heterosystems

Structurally diverse spiroheterocycles incorporating medicinally privileged heterosystems have been synthesized by a simple and convenient synthesis involving triethylamine catalyzed multicomponent domino reaction of 2-aminobenzothiazoles with isatin and cyclic 1,3-diketones.     

Synthesis and characterization of LaB6 thin films on tungsten, rhenium, silicon and other substrates and their investigations as?field emitters

The paper deals with the comparative study of nanocrystalline Lanthanum hexaboride (LaB₆) thin films grown on various substrates by Pulsed laser deposition and Arc plasma method. Field emission studies were carried out on LaB₆ films deposited on various substrates show metallic behavior of the emitters. The high value of field enhancement factors, indicating that the electron emission from LaB₆ nanoscale protrusions deposited on emitter surface. The post field emission surface morphology of the emitters showed no significant erosion of the films during continuous operation. The observed behavior indicates that it is linked with the growth of LaB₆ films on substrate crystal structure. The LaB₆ nanocrystallites/nanowires films were synthesized using arc plasma method shows good emission current stability. The LaB₆ micro/nanocrystallites were also obtained by picosecond laser irradiation which gives high enhancement β factor, and good emission current stability along with high current density. The results reveal that nanocrystalline LaB₆ films, exhibit high resistance to ion bombardment and excellent structural stability and are more promising emitters for practical applications in field emission based new generation devices.     

Shape factor for bermed wall

This note reports the dependence of shape factor corresponding to the portion of wall behind a berm and above the ground on the angle of berm; the results have been obtained by thermal simulation of heat transfer between the ground and the wall through the berming.     

Field theoretic calculation of energy cascade rates in non-helical magnetohydrodynamic turbulence

Energy cascade rates and Kolmogorov’s constant for non-helical steady magnetohydrodynamic turbulence have been calculated by solving the flux equations to the first order in perturbation. For zero cross helicity and space dimensiond = 3, magnetic energy cascades from large length-scales to small length-scales (forward cascade). In addition, there are energy fluxes from large-scale magnetic field to small-scale velocity field, large-scale velocity field to small-scale magnetic field, and large-scale velocity field to large-scale magnetic field. Kolmogorov’s constant for magnetohydrodynamics is approximately equal to that for fluid turbulence (≈ 1.6) for Alfvén ratio 05 ≤r _A ≤ ∞. For higher space-dimensions, the energy fluxes are qualitatively similar, and Kolmogorov’s constant varies asd ^1/3. For the normalized cross helicity σ_c →1, the cascade rates are proportional to (1 − σ_c)/(1 + σ_c , and the Kolmogorov’s constants vary significantly with σ_cc.     

Clionasterol Glucoside and Acylated Clionasterol Glucosides from Oplismenus burmannii

A new clionasterol glucoside, clionasterol‐[(1'→3α)‐O‐β‐D]‐glucopyranoside ( 1 ), a new acylated clionasterol glucoside, clionasterol‐[6'‐O‐acyl‐(1'→3β)‐O‐b‐D]‐glucopyranoside ( 2 ) and clionasterol ( 3 ) were isolated from the aerial parts of Oplismenus burmannii. The nature and length of fatty acid acyl chains in 2 was identified by alkaline methanolysis of compound 2 . The aglycone fraction on GC‐MS analysis showed three peaks in GC at t_R 49.86 (82.1%), 51.13 (13.3%) and 56.53 (4.6%) min, which were characterized as arachidic acid methyl ester ( a ) oleic acid methyl ester ( b ) and 12‐methyltetradecanoic acid methyl ester ( c ) respectively. Thus 2 was characterized as a mixture of three new compounds, clionasterol‐[6'‐O‐eicosanoyl‐(1'→3β)‐O‐β‐D]‐glucopyranoside ( 2a ), clionasterol‐[6'‐O‐(8Z)‐octa‐deca‐9‐enoyl‐(1'→3β)‐O‐β‐D]‐glucopyranoside ( 2b ) and clionasterol‐[6'‐O‐(12‐methyltetradecanoyl)‐(1'→3β)‐O‐β‐D]‐glucopyranoside ( 2c ).