Halogenation effects on the conformational properties of alkanes

The rotational barriers of the CC bonds of halocarbons are believed to be rather different than those of hydrocarbons. We wish to systematically study the effect of halogen substituents on the conformational flexibility of hydrocarbons. As our initial approach to this problem, we have synthesized the following molecules: Pyrene-(CF₂)_n-Pyrene (n=3, 4, and 6) and Pyrene-(CF₂)_n-F (n=4 and 6). We describe here the concentration and temperature dependence of the emissive behavior of these materials.     

On the dispersion of a solute in oscillating flow of a non-Newtonian fluid in a channel

The paper presents an exact analysis of the dispersion of an immiscible solute in a non-Newtonian fluid (known as an incompressible second-order fluid which shows viscoelastic behaviour) flowing slowly in a parallel plate channel in the presence of a periodic pressure gradient. Using a generalized dispersion model which is valid for all times after the solute injection, the diffusion coefficients K _i (τ)(i=1,2,3,…) are obtained as functions of time τ in the case when the initial solute distribution is in the form of a slug of finite extent. The analysis leads to the novel result that K ₂(τ) (which is a measure of the longitudinal dispersion coefficient of the solute) has a steady part S in addition to a fluctuating part D ₂(τ) due to the pulsatility of the flow. It is found that S decreases with increase in the viscoelastic parameter M for given values of the amplitude λ and frequency ω of the pressure pulsation. On the other hand, it is found that at a fixed instant τ, the amplitude of D ₂(τ) increases with increase in M for given values of λ and ω. Further it is shown that at a given instant τ, the amplitude of D ₂(τ) decreases with increase in ω for given λ and M and the profile for D ₂(τ) becomes progressively flatter with increase in ω. Finally the axial distribution of the average concentration θ _m of the solute over the channel cross-section is determined at different instants after the solute injection for several values of M, λ and ω. The present study is likely to have important bearing on the problem of dispersion of tracers in blood flow through arteries.     

FLUORESCENCE STUDIES WITH HUMAN EPIDERMAL GROWTH FACTOR

Steady-state and time-resolved fluorescence studies have been performed with human epidermal growth factor, a small globular protein having two adjacent tryptophan residues near its C-terminus. Based on the relatively red fluorescence and accessibility to solute quenchers, the two tryptophan residues are found to be exposed to solvent. Anisotropy decay measurements show the dominant depolarizing process to have a sub-nanosecond rotational correlation time indicating the existence of rapid segmental motion of the fluorescing tryptophan residues. From an analysis of the low-temperature excitation anisotropy spectrum of the protein (and in comparison with that of tryptophan, the peptide melittin, and the dipeptide trp-trp), it is concluded that homo-energy transfer and/or exciton interaction occurs between the adjacent tryptophan residues. A thermal transition in the structure of the protein, which is observed by circular dichroism measurements, is not sensed by the steady-state fluorescence of the protein. This result, in conjunction with the anisotropy decay results, indicates that the two tryptophan residues are in a highly flexible C-terminus segment, which is not an integral part of the three-dimensional structure of the protein. Fluorescence measurements with three site-directed mutants also show very little variation.     

Photopolymerization of methyl methacrylate using a combination of rhodamine 6G and benzoyl peroxide as photoinitiator in nonaqueous media

Photopolymerization of methyl methacrylate (MMA) in visible light was studied at 40°C using Rhodamine 6G—Benzoyl peroxide combination as photoinitiator. The photopolymerization proceeds by a free radical mechanism and the radical generation process occurs by an initial complexation reaction between the initiator components. Kinetic data indicated a lower-order dependence of R_p on initiator concentrations (initiator exponent < 0.5). Initiator-dependent chain termination was significant along with the bimolecular mode of chain termination.     

Large-scale fabrication of aligned single-walled carbon nanotube array and hierarchical single-walled carbon nanotube assembly

Aligned single-walled carbon nanotubes (SWNTs) and hierarchical SWNT assembly were fabricated by electrospinning. The high fiber elongation and high DC electric field applied during the electrospinning process result in the orientation of the SWNTs along the axial direction of the fiber. The alignment of the electropsun composite fiber transfers this local SWNT orientation to macroscopically aligned SWNTs. After removing the polymer component from the aligned composite fiber, we produced large area aligned SWNTs. The results show that the directional control of SWNT alignment and debundling of SWNTs into individual tubes can be simultaneously realized.     

Reactions of fluorinated acid anhydrides, (CF3CO)2O, (CF3SO2)2O and (FSO2)2O, with organometallic substrates of group 15 (As, Sb and Bi)

(C₆H₅)₃MX₂ (M = As, Sb; X = OCOCF₃ and M = Sb, Bi; X = SO₃F, SO₃CF₃) compounds prepared by the interaction of triphenylmetal(V) substrates with (CF₃CO)₂O, (CF₃SO₂)₂O and (FSO₂)₂O have been characterized by molecular weight determination, elemental and spectroscopic (IR, ¹H and ¹⁹F NMR, mass) analyses.     

Detecting stop consonants in continuous speech

The problem of implementing a detector for stop consonants in continuously spoken speech is considered. The problem is posed as one of finding an optimal filter (linear or nonlinear) that operates on a particular appropriately chosen representation, and ideally outputs a 1 when a stop occurs and 0 otherwise. The performance of several variants of a canonical stop detector is discussed and its implications for human and machine speech recognition is considered.