Electrochemical Properties of Carbon Nanoparticles Entrapped in Silica Matrix

Carbon-based electrode materials have been widely used for many years for electrochemical charge storage, energy generation, and catalysis. We have developed an electrode material with high specific capacitance by entrapping graphite nanoparticles into a sol-gel network. Films from the resulting colloidal suspensions were highly porous due to the removal of the entrapped organic solvents from sol-gel matrix giving rise to high Brunauer-Emmett-Teller (BET) specific surface areas (654 m(2)/g) and a high capacitance density ( approximately 37 F/g). An exponential increase of capacitance was observed with decreasing scan rates in cyclic voltammetry studies on these films suggesting the presence of pores ranging from micro (< 2 nm) to mesopores. BET surface analysis and scanning electron microscope images of these films also confirmed the presence of the micropores as well as mesopores. A steep drop in the double layer capacitance with polar electrolytes was observed when the films were rendered hydrophilic upon exposure to a mild oxygen plasma. We propose a model whereby the microporous hydrophobic sol-gel matrix perturbs the hydration of ions which moves ions closer to the graphite nanoparticles and consequently increase the capacitance of the film.     

Kinetics and mechanism of dissociation of some tri- and tetra-dentate complexes of copper(II) in acid media

Summary Kinetics of the dissociation ofm-phenylene-dibiguanidecopper(II) ion,N-salicylideneglycyl-glycinatocuprate(II) ion andN-salicylideneglycinato-aquocopper(II) in acid media, forming aquo-copper(II) ion, have been studied by the stopped-flow spectrophotometric technique. Dissociation of the complexes occurs in two consecutive steps, the first being faster than the second. For them-phenylenedibiguanide complex each step exhibits second order acid dependance,k _x=k _x [H⁺]² wherek _x is the observed pseudo-first order rate constant. However, the Schiff base complexes show first order acid dependance,k _x=k _x [H⁺], for both steps. The results, with relatively low H and highly negative S values, are consistent with a solvent-assisted dissociative process.     

Importance of solute–solute interactions on glass formability

Microalloying experiments on amorphous Al₈₄La₄Er₂Ni₈TM₂ alloys were performed with the substitution of all 3d TM (transition metal) elements and one 4d TM element. The critical thickness of the amorphous alloys was used as a criterion for glass formability in this system. The results show that, other than atomic size differences and the negative heats of mixing among the solvent and solute atoms, the atomic interactions among the solute atoms play an important role on glass formation. When the solute–solute interaction becomes repulsive (positive heat of mixing), glass formability suffers. Similarly, when the solute–solute interaction becomes highly attractive, exceeding that between the solvent and solute atoms, glass formability is also degraded. Evaluation of a large number of known multicomponent bulk metallic glasses provides additional support to these conjectures. This study shows that the solute–solute interaction plays an important role in glass formation, which has not been recognized previously.     

Hawking radiation from black holes in de Sitter spaces via covariant anomalies

We apply the covariant anomaly cancellation method to compute the Hawking fluxes from the event and cosmic horizons of the Schwarzschild–de Sitter black hole. The derivation is new from the existing ones as we split the space in three different regions (near to and away from the event and cosmic horizons) and write down the covariant energy–momentum tensor using three step functions which covers the whole region leading elegantly to the conditions required to compute the Hawking fluxes from the event and cosmic horizons.     

Antioxidant activity guided separation of major polyphenols of marjoram (Origanum majorana L.) using flash chromatography and their identification by liquid chromatography coupled with electrospray ionization tandem mass spectrometry†

Marjoram extracts have been separated into polar and nonpolar parts using liquid–liquid extraction. Both polar and nonpolar parts of the extracts were further fractionated by flash chromatography. The obtained fractions (90 polar and 45 nonpolar fractions) were investigated for their antioxidant activities by 2,2‐diphenylpicrylhydrazyl and ferric ion reducing antioxidant power assays. A direct, positive, and linear relationship between antioxidant activity and total phenolic content of the fractions was observed. Based on antioxidant and total phenolic content data, the three fractions with the high antioxidant activities from polar and nonpolar part of the extract were analyzed for their constituent polyphenols by liquid chromatography coupled with electrospray ionization tandem mass spectrometry. Compounds were identified by matching the mass spectral data and retention time with those of authentic standards. Identification of the compounds for which there were no “in‐house” standards available was carried out by accurate mass measurement of the precursor ions and product ions generated from collision‐induced dissociation. Rosmarinic acid was found to be the strongest antioxidant polyphenol conferring the highest antioxidant activity to fractions 47 and 17 of polar and nonpolar part of the extract, respectively. The identification of the rosmarinic acid was further confirmed by ¹H NMR spectroscopy.     

Simultaneous demodulation and dispersion compensation of WDM DPSK channels using optical ring resonator

We have introduced and comprehensively analyzed a novel scheme of simultaneous demodulation and dispersion compensation of wavelength division multiplexed (WDM) non-return-to zero (NRZ) differential phase shift keying (DPSK) optical link using an optical ring resonator (ORR) based filter. Using extensive numerical simulation we have demonstrated the transmission of 10.7 Gb/s WDM DPSK channels having 50 GHz and 100 GHz spacing over 400 km of unrepeatered reach at 20 dB optical-signal-to-noise-ratio (OSNR) to achieve a bit error rate (BER) of 10^? 3.     

Stochastic theory of interfacial enzyme kinetics: A kinetic Monte Carlo study

In the spirit of Gillespie’s stochastic approach we have formulated a theory to explore the advancement of the interfacial enzyme kinetics at the single enzyme level which is ultimately utilized to obtain the ensemble average macroscopic feature, lag-burst kinetics. We have provided a theory of the transition from the lag phase to the burst phase kinetics by considering the gradual development of electrostatic interaction among the positively charged enzyme and negatively charged product molecules deposited on the phospholipid surface. It is shown that the different diffusion time scales of the enzyme over the fluid and product regions are responsible for the memory effect in the correlation of successive turnover events of the hopping mode in the single trajectory analysis which again is reflected on the non-Gaussian distribution of turnover times on the macroscopic kinetics in the lag phase unlike the burst phase kinetics.