Ultrafast intermolecular electron transfer dynamics: Perylene in electron-accepting micellar medium

The dynamics of ultrafast photoinduced intermolecular electron transfer (ET) from the excited singlet (S1) state of perylene (Pe) to an electron-accepting cationic surfactant molecule, N-cetylpyridinium chloride (CPC), in aqueous micellar solutions has been investigated using the femtosecond transient absorption spectroscopic technique with temporal resolution of 120 fs. The Pe molecule is localized at or near the micellar surface, where it coexists with the pyridinium moieties (headgroups of the micelle) of the surfactant molecule. Following photoexcitation of Pe, an electron is transferred to the neat and geometrically restricted headgroup of the micelle. Dynamics of the forward ET process as well as the geminate recombination or back ET (BET) process have been followed by monitoring the temporal evolution of the S1 state of Pe and the cation radical of Pe (Pe*+), respectively. The multiexponential forward ET process indicates that the ET dynamics is highly correlated with the spatial distributions of the micellar headgroups around a donor Pe molecule and thus dependent on the donor-acceptor distance. The distance-dependent ET and BET rates have been calculated following the method of Weidemaier and Fayer (J. Chem. Phys. 1995, 102, 3820) to get the best fit parameters for the multiexponetial temporal profiles for the S1 state of Pe as well as Pe*+. Because the acceptor is a constituent of the neat micellar medium, their confinement on the surface of the microheterogeneous medium provides a very large concentration such that, even though the forward transfer rate is 0.06 ps(-1) at the distance of closest approach, the ET process is complete within a 200-ps time domain. If the concepts of distribution of ET distances are utilized, the possible role of material diffusion on the kinetics of forward ET is ruled out. This is an experimental study to show, for the first time, the ultrafast distance-dependent light-induced ET dynamics following both the excited state of the donor and the cation radical formed in an ET process using the transient absorption spectroscopic technique in a self-reactive restrictive environment.     

Dimethylthiocarbamate (DMTC): an alcohol protecting group

Dimethylthiocarbamates (DMTCs), prepared from the corresponding alcohols using commercial dimethylthiocarbamoyl chloride, are spectrally simple, achiral, and nonpolar. DMTCs are moderately to highly stable to a wide range of reagents and conditions including metal hydrides, hydroboration, ylides, NaOH, HCl, organolithiums, Grignards, DDQ, PCC, Swern, n-Bu(4)NF, CrCl(2), heat, and Lewis acids. They are readily removed by NaIO(4) or H(2)O(2) in the presence of other common alcohol protecting groups. [structure: see text]     

Study of gain flatness for multi-channel amplification in single stage EDFA for WDM applications

In this paper, gain flatness is studied for simultaneous 16-ITU-T channel amplifications at C-band (1,532–1,558 nm) in a single stage EDFA for WDM application at different average inversion levels. The inversion levels are varied due to the change of the input signal levels from the targeted operating point and also for dropping few numbers of channels. Specially designed gain flattening filter (GFF) is used in order to get the flat gain with gain variation ±0.5 dB for −20 dBm/ch input signal power (total input signal power is −8.0 dBm) at a fixed average inversion level which is maintained by proper selection of optimum fibre length and pump power. A specific loss spectrum of GFF is obtained by writing a chirped fibre Bragg grating of length 20 mm. Gain variations are studied by changing the total input signal levels from −8.0 dBm to −20.0 dBm and maintained within 20.0 ± 0.5 dB by using automatic gain control (AGC) circuit. About 15 out of 16 channels are dropped and observed ± 0.5 dB gain-variation which is an important parameter in optical network system.     

Effect of time delay on a harvested predator-prey model

The predator-prey systems with harvesting have received a great deal of attentions for last few decades. Incorporating discrete time delays into predator-prey models could induce instability and bifurcation. In this paper we are interested in studying the combined effects of harvesting and discrete time delay on the dynamics of a predator-prey model. A comparative analysis is provided for stability behaviour in absence as well as in presence of time delay. The length of discrete time delay to preserve stability of the model system is obtained. Existence of Hopf-bifurcating small amplitude periodic solutions is derived by taking discrete time delay as a bifurcation parameter.     

Sulfonation of metallocene‐based polyolefinic elastomers and its influence on physicomechanical properties: Effect of reaction parameters,styrene grafting,and pendant chain length

Direct sulfonation and styrene‐mediated sulfonation were carried out onto metallocene‐based poly(ethylene‐co‐octene) (POE) and poly(ethylene‐co‐butene) (PBE) elastomers to impart polarity on the completely nonpolar rubbery matrices and to prepare a new class of elastomer. The influence of styrene‐grafting and pendant chain length on the degree of sulfonation was also studied. The effects of sulfonation, styrene grafting and styrene‐mediated sulfonation at their optimized levels on various physicomechanical properties were thoroughly investigated, and the resultant properties were correlated with structures of the modified elastomers. Higher extent of sulfonic acid groups were introduced through direct sulfonation in comparison with the styrene‐mediated sulfonation, whereas better thermal and mechanical properties were obtained through styrene‐mediated sulfonation in comparison with the direct sulfonation process. PBE had shown higher degree of sulfonation and percentage grafting than POE. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8023–8040, 2008     

Spin-orbit gauge and quantum spin Hall effect

We have shown that the non-Abelian spin-orbit gauge field strength of the Rashba and Dresselhaus interactions, when split into two Abelian field strengths, the Hamiltonian of the system can be re-expressed as a Landau level problem with a particular relation between the two coupling parameters. The quantum levels are created with up and down spins with opposite chirality and leads to the quantum spin Hall effect.     

Synthesis,structure and antibacterial activity of manganese(III) complexes of a Schiff base derived from furfurylamine

Two new mononuclear complexes of manganese(III) viz. [MnL₂(LH)₂]ClO₄ (1) and [MnL₂(N₃)]·0.5CH₃OH (2) have been synthesized by reacting manganese perchlorate with furfurylamine and salicylaldehyde (plus sodium azide in 2) where L = (2-hydroxybenzyl-2-furylmethyl)imine, an asymmetric bidentate Schiff base formed in situ to bind the Mn(III) ion. The complexes have been characterized by elemental analysis, IR spectroscopy, TGA and single crystal X-ray diffraction studies. Structural studies reveal that the complexes 1 and 2 adopt an octahedral and a square pyramidal geometry, respectively. The antibacterial activity of the complexes has been tested against Gram(+) and Gram(?) bacteria.     

A reflection-type oil-film skin-friction meter

Tanner has shown analytically that the slope characteristics of a thin oil-film lying in contact with a surface on which an aerodynamic boundary-layer is developing are explicitly related to the local skin-friction. Unlike many conventional methods of measuring skin-friction, the oil-film method is absolute in nature, requires no calibration and in principle, can be universally applied. In all existing forms of the meter, however, interferometry is used to make measurements of the oil film. In the present contribution, the technique has been simplified by completely eliminating interferometry. This has been achieved by making direct and dynamic measurements of the oil-film slope by directing a reflected beam of light off the top of the oil film to a small position sensing photodiode. The raw data now is very different from that in the interferometric method and consequently, new methods of determining skin-friction from measured oil-film slope histories have been developed. The reflection method has been verified in incompressible flat plate turbulent boundary-layers. The standard of deviation of the measurements is about 10% of the mean. The present version of the meter is compact and simple.