A New Tetrahydrofurannulation Via Tandem Radical Cyclization Reaction-Reductive Deoxygenation Sequence

Treatment of bromoketals 2, derived from allyl alcohols 1, with tributyltin chloride, sodium cyanoborohydride and AIBN furnishes the tetrahydrofurannulated products 3 via a 5-exo-trig radical cyclisation reaction followed by reductive cleavage of ketal 4.

Time-Resolved Resonance Raman Spectroscopic Studies on the Radical Anions of Menaquinone and Naphthoquinone

Quinones and their radical ion intermediates have been much studied by vibrational spectroscopy to understand their structure-function relationships in various biological processes. In this paper, we present a comprehensive analysis of vibrational spectra in the structure-sensitive region of both the naphthoquinone (NQ) and 2-methyl-1,4-naphthoquinone (MQ, menaquinone) radical anions using time-resolved resonance Raman and ab initio studies. Specific vibrational mode assignments have been made to all the vibrational frequencies recorded in the experiment. It is observed that the carbonyl and C-C stretching frequencies show considerable coupling in NQ and MQ radical anions. Further, the asymmetric substitution present in MQ with respect to NQ shows important signatures in the radical anion spectrum. It is concluded that assignments of vibrational frequencies of asymmetrically substituted quinones must take into consideration the influence of asymmetry on structure and reactivity.

Formal total synthesis of 2-pupukeanone via radical mediated cyclisation of an enyne

Diels-Alder reaction of the dienone 12, obtained by C-alkylation of sodium 2,6-dimethylphenoxide, with acrylonitrile and phenyl vinyl sulfones generate the enynes 14 and 17. Tributyltin radical addition to the terminal acetylene in 14 and 17 lead to the vinylstannanes 15 and 18 via 5-exo trig cyclisation of the resulting vinyl radical, which on oxidative cleavage furnishes the isotwistane-diones 16 and 19. Reductive desulfonylation of the diketosulfone 19 furnishes the dione 11, constituting a formal total synthesis of 2-pupukeanone 5 and 2-isocyanopupukeanone 3.

Bridged systems via radical cyclization reactions. Stereospecific synthesis of chiral tricyclo[6.2.1.0(1,5)]undecanes

The application of radical-mediated cyclizations and annulations in organic synthesis has grown in importance steadily over the years to reach the present status where they are now routinely used in the strategy-level planning.2 The presence of a quaternary carbon atom is frequently encountered in terpenoid natural products, and it often creates a synthetic challenge when two or more quaternary carbon atoms are present in a contiguous manner.3 Even though creation of a quaternary carbon atom by employing a tertiary radical is very facile, creation of a quaternary carbon atom (or a spiro carbon atom) via radical addition onto a fully substituted olefinic carbon atom is not that common but of synthetic importance. For example, the primary radical derived from the bromide 1 failed to cyclize to generate the two vicinal quaternary carbon atoms and resulted in only the reduced product 2.4 The tricyclic carbon framework tricyclo[6.2.1.01,5]undecane (3) is present in a number of sesquiterpenoids e.g. zizzanes, prelacinanes, etc.5

Depth profile composition studies of thin film CdS: Cu,S solar cells using XPS and AES

Surface composition and depth profile studies of hemiplated thin film CdS:CuzS solar cells have been carried out using x-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) techniques. These studies indicate that the junction is fairly diffused in the as-prepared cell. However, heat treatment of the cell at 210°C in air relatively sharpens the junction and improves the cell performance. Using the Cu(2p3p)/S(2p) ratio as well as the Cu(LVV)/(LMM) Auger intensity ratio, it can be inferred that the nominal valency of copper in the layers above the junction is Cut and it is essentially in the CUSS form. Copper signals are observed from layers deep down in the cell. These seem to appear mostly from the grain boundary region. From the observed concentration of Cd, Cu and S in these deeper layers and the Cu(LVV)/(LMM) ratio it appears that the signals from copper essentially originate partly from copper in CuS and partly from Cu2t trapped in the lattice. It is significant to note that the nominal valence state of copper changes rather abruptly from Cut to Cuz+ across the junction.

A Radical Cyclization Route To +/-Andirolactone, A Spiro-Gamma-Butyrolactone

Synthesis of Andirolactone (Image ), starting from 4-methyl cyclohex-3-en-1-one (Image ), via the radical cyclisation of the bromoacetal (Image ), is described.

Trimming studies on polymer thick-film resistors

PVC-graphite polymer thick-film resistors were trimmed by a conventional air abrasive technique and the post-trim drift in resistance with time was found to be negative. The net decrease in resistance of trimmed resistors in a given time was found to be a function of resistor composition, cutting speed and temperature. Detailed studies showed this decrease to be due to a decrease in cut width with time. Two new methods, namely bombardment trimming and radiation trimming, were also tried for adjusting the resistance of these resistors and the results were compared with those obtained from abrasive trimming studies.

Film cooling at hypersonic Mach numbers using forward facing array of micro-jets

Experimental investigations are carried out in the IISc hypersonic shock tunnel on film cooling effectiveness of a single jet (diameter 2 mm and 0.9 mm), and an array forward facing of micro-jets (diameter 300 mu m each) of same effective area (corresponding to the respective single jet). The single jet and the corresponding micro-jets are injected from the stagnation zone of a blunt cone model (58, apex angle and nose radius of 35 mm). Nitrogen and Helium are injected as coolant gases. Experiments are performed at freestream Mach number 5.9, at 0 degrees angle of attack, with a stagnation enthalpy of 1.84 MJ/kg, with and without injections. The ratios of the jet stagnation pressure to the freestream pitot pressure used in the present study are 1.2 and 1.45. Up to 50% reduction in surface heat transfer rate was observed with the array of micro-jets, compared to that of the respective single jet with nitrogen as the coolant, while the corresponding eduction was up to 37% for helium injection, with the schlieren flow visualizations showing no major change in the shock standoff distance, and thus no major changes in other aerodynamic aspects such as drag.

Inhibition of H2O2 generation in rat liver mitochondria by radical quenchers and phenolic compounds

Generation of H2O2 by rat liver mitochondria with choline, glycerol 1-phosphate and proline as substrates has been shown by using high-concentration phosphate buffer. Rates obtained under these conditions were higher and more consistent as compared with the earlier reports with high-concentration mannitol/sucrose/Tris buffer. Sulphate ions could replace phosphate indicating a requirement for a high concentration of oxygen-containing anions. H2O2 generation was dependent on the presence of native mitochondria and substrate. Maximal rates with various substrates were found to be the same as with succinate. Values of Km and Vmax for H2O2 generation were considerably less than those obtained for respective dehydrogenase activities, measured by dye reduction. Scavengers of O2-. and OH. inhibited generation of H2O2. ATP, ADP, thyronine derivatives and a number of phenolic compounds also showed very potent inhibitory effects of H2O2 generation, whereas phenyl compound had no effect. Phenolic compounds did not have any effect on mitochondrial superoxide dismutase and choline dehydrogenase activities as well as on O2-. generation by the xanthine-xanthine oxidase system. Inhibition by phenolic compounds may have potential for regulation of the intracellular concentration of H2O2, that is not considered to have a "second messenger' function.

Effect of inclination on laminar film condensation

The effect of inclination on laminar film condensation over and under isothermal flat plates is investigated analytically. The complete set of Navier Stokes equations in two dimensions is considered. Analysed as a perturbation problem, the zero-order perturbation represents the boundary layer equations. First and second order perturbations are solved to bring about the leading edge effects. Corresponding velocity and temperature profiles are presented. The results show decrease in heat transfer with larger ∥inclinations∥ from the vertical. Comparison with experimental data of Gerstmann and Griffith indicates a closer agreement of the present results than the analytical results of the same authors.

Analysis and computation of the oil film thickness between the piston ring and cylinder liner of an internal combustion engine

A study of the essential features of piston rings in the cylinder liner of an internal combustion engine reveals that the lubrication problem posed by it is basically that of a slider bearing. According to steady-flow-hydrodynamics, viz. Image the oil film thickness becomes zero at the dead centre positions as the velocity, U = 0. In practice, however, such a phenomenon cannot be supported by consideration of the wear rates of pistion rings and cylinder liners. This can be explained by including the “squeeze” action term in the

On uniformity of film thickness on rotating substrates having a large source-to-substrate height

Abstract is not available.

Uniformity of film thickness on rotating planetary planar substrates

For the purposes of obtaining a number of components with nearly identical thickness distributions over the substrate area and of minimizing the inhomogeneities of the film, it is logical to presume that a substrate rotating on its own axis and revolving around another axis will give more uniformity in film thickness than a substrate only revolving around one axis. In relation to the practical applications, an investigation has been undertaken to study the refinement that can be achieved by using a planar planetary substrate holder. It is shown theoretically that the use of the planetary substrate holder under ideal conditions of source and geometry does not offer any further improvement in uniformity of thickness over the conventional rotary work-holder. It is also shown that the geometrical parameters alone have little influence over the uniformity achieved on a planetary substrate, because of the complex cyclidal motion of any point on it. However, for any given geometry, a non-integral speed ratio of the planetary substrate and the work-holder shows considerably less variation in thickness over the substrate area.