Cobalt-catalyzed oxidative esterification of allylic/benzylic C(sp3)–H bonds

A protocol for the cobalt-catalyzed oxidative esterification of allylic/benzylic C(sp³)–H bonds with carboxylic acids was developed in this work. Mechanistic studies revealed that C(sp³)–H bond activation in the hydrocarbon was the turnover-limiting step and the in-situ formed [Co(III)]Ot-Bu did not engage in hydrogen atom abstraction (HAA) of a C–H bond. This protocol was successfully incorporated into a synthetic pathway to β-damascenone that avoided the use of NBS.     

Laser Induced Surface Morphology of Molybdenum Correlated with Breakdown Spectroscopy

Surface modifications of laser irradiated molybdenum have been correlated with plasma parameters. Nd:YAG laser (1064 nm, 10 ns) was employed at various laser irradiances ranging from 6 to 50 GW/cm² under argon environment. The ablation efficiency has been investigated by measuring the crater depth using surface profilometry analysis. Scanning electron microscope (SEM) analysis reveals the formation of coarse grains along with cracked boundaries, cavities and cones at the central ablated areas. Whereas, uplifted re-solidified material, cavities, ridges, droplets and cones were observed at boundary regions. Laser Induced Breakdown Spectroscopy (LIBS) analysis has been performed to evaluate electron temperature and number density of molybdenum plasma. Electron temperature and electron density varies from 6670 to 9305 K and 0.62 × 10¹⁸ to 0.72 × 10¹⁸ cm^?3 respectively. Both the parameters showed similar trend in variation with laser irradiance i.e. an initial increase from 13 to 19 GW/cm² followed by a decrease from 19 to 25 GW/cm² and then a saturation from 25 to 50 GW/cm². The initial increasing trend is attributed to the enhanced excited vapor content of the ablated material, confinement effects of the surrounding argon and absorption of laser energy into the molybdenum vapor plasma during the trailing part of laser pulse leading to ignition of laser supported combustion (LSW) waves. The decreasing trend is attributed to the shielding effect and saturation is explainable on the basis of the formation of a self-regulating regime. Surface modifications of laser irradiated molybdenum were correlated with the plasma parameters.     

Synthesis and characterization of ion‐conducting polymer systems based on EPDM blends

This work reports the preparation and characterization of new polymeric ionomers based on etylene–propylene–diene copolymer (EPDM) with a high norbornene content. The sulfonation level was determined with X‐ray photoelectron spectroscopy, and the microstructural characterization was obtained through differential scanning calorimetry and dynamic mechanical analysis. In addition, the effects of certain plasticizers and polymers on the microstructures and conducting properties of these materials were studied, with special attention paid to the latter because of the interest aroused by these materials as membranes in polymer fuel cells. On the basis of the results, some of the synthesized membranes could be used for fuel cells because of their high conductivity (≥10^?2 S/cm) and good dimensional stability (any shrinkage observed). © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 1017–1026, 2001     

Interaction of some antioxidants with Belousov-Zhabotinsky reaction based on catechol-BrO 3 − -Mn2+-H2SO4 system

Temporal evolution of a new Mn(II) catalyzed Belousov-Zhabotinsky (BZ) chemical oscillator with catechol (1.2-dihydroxybenzene) as organic substrate is reported within narrow range of concentrations of initial reagents at 30°C. After optimizing the oscillation parameters the system was perturbed with the antioxidants like ascorbic acid and inosine. It is found that ascorbic acid acts as co-substrate within certain concentration limit, whereas inosine acts as a quencher of oscillations. Addition of ascorbic acid to the BZ system decreases induction time thus acting synergistically to help the reaction to enter quickly into the oscillatory regime. A good linear dependence of induction time on the concentration of ascorbic acid (R ² = 0.9948) and inosine (R ² = 0.955) is reported. Inosine has been found to increase the induction time and quench the oscillations. It is mentioned that the magnitude of induction time decreases to a greater extent with ascorbic acid as compared to the magnitude of its increase with the same concentration of inosine. This is pointing to the fact that ascorbic acid is stronger antioxidant than inosine as depicted by their interaction with catechol-based BZ chemical oscillator. Temporal evolution of the BZ reaction with the injection of antioxidants at different stages of reaction is also reported.     

Existence of approximate solutions of the forced Duffing equation with discontinuous type integral boundary conditions

We develop a generalized quasilinearization technique to obtain a sequence of approximate solutions converging monotonically and quadratically to the unique solution of the forced Duffing equation with discontinuous type integral boundary conditions.     

Amphiphilic drug persuaded collapse of polyvinylpyrrolidone and poly(ethylene glycol) chains: A dynamic light scattering study

Light scattering has proved to be useful in characterizing colloidal systems. We have studied the interaction between an amphiphilic drug, amitriptyline hydrochloride (AMT), and neutral polymers, polyvinylpyrrolidone (PVP) and poly(ethylene glycol) (PEG), using the dynamic light scattering (DLS) technique. AMT was found to interact with PVP more strongly than PEG. A large decrease of the size of aggregates upon increase of AMT concentration indicates a successive collapse of the polymer conformation. The partial negatively charged oxygen atoms, present in the amide group of PVP, were believed to be responsible for the collapse while interacting with the cationic head group of AMT. Presence of NaBr in the solution enhanced the effect markedly and made the AMT–PVP aggregates more compact. The PEG aggregates also showed a similar behavior, although less pronounced than the PVP. The results obtained in the present investigations may be helpful to design the drug delivery systems for the antidepressant drugs as the higher concentration of these drugs is harmful for the human body. Likewise, as the results have shown that on increasing the temperature there is a decrease in the extent of interaction; this may be helpful for the controlled release formulations.     

Methodology to determine the impact of linewidth variation on chip scale copper/low-k backend dielectric breakdown

Low-k time-dependent dielectric breakdown (TDDB) has been found to be a function of metal linewidth, when the distance between the lines is constant. Modeling requires determining the relationship between TDDB and layout geometries. To determine this relationship, comb test structures have been design and implemented in 45 nm technology. In this work, low-k dielectric breakdown, low-k dielectric vulnerable areas, and linewidth variation are linked to full chip lifetimes.