The Ã1B2-X̃1A1 two-photon fluorescence excitation spectrum of 1,3-difluorobenzene

The $\text{A}\text{?}{}^1\text{B}{}_2\text{-}\text{X}\text{?}{}^1\text{A}{}_1$ system of 1,3-difluorobenzene has been observed using the technique of two-photon fluorescence excitation obtained with a pulsed dye laser. Calibration was achieved by a combination of the neon optogalvanic spectrum and etalon fringes. In circular, compared to linear, polarization the bands divide into two groups, those which are B₂-A₁ and which retain their intensity with circular polarization, and those which are A₁-A₁ and lose about 60% of their intensity under the same conditions. These two kinds of bands also show characteristic rotational contours. All of the A₁-A₁ bands whose assignments are established obtain their intensity through vibronic interaction in which the vibration ν′₂₅ (ν′₁₄ in the Wilson numbering) mixes the $\text{A}\text{?}$ with, presumably, the $\text{X}\text{?}$ state. There is an important Fermi resonance between the 9¹ and 10¹11¹ levels. Parts of the one-photon absorption spectrum have been photographed to identify sequences associated with the 0₀⁰ band for comparison with those observed in the two-photon spectrum, and to search for bands involving odd quanta of b₂ vibrations, including ν′₂₅ (ν′₁₄); none was found.     

Short-Term Effects of Endotracheal Intubation on Voice

The objective of this study was to examine the vocal symptoms and acoustic changes perceived in the short period after endotracheal intubation, and to find the association between these changes and the endotracheal tube parameters. A total of 35 subjects were included. They were examined preoperatively, and 2 and 24 hours postoperatively. The vocal symptoms of hoarseness, vocal fatigue, loss of voice, throat clearing, globus pharyngeus, throat pain, and the acoustic variables mainly average fundamental frequency, relative average perturbation, shimmer, noise to harmony ratio, voice turbulence index, habitual pitch, and maximum phonation time (MPT) were assessed as such and in relation to the following endotracheal tube parameters: duration of anesthesia, number of intubation attempts, size of the tube, cuff volume, cuff mean pressure, and the emergence. The association between anesthesia parameters with incidence of vocal complaints and changes in acoustic parameters were examined using logistic and linear regression. Vocal fatigue was associated significantly with the increase in cuff volume and the number of intubation attempts. Throat clearing was associated significantly with the increase in cuff mean pressure. Only the increase in habitual pitch was associated significantly with the increase in cuff volume. The acute short-term effect of endotracheal intubation on voice is significant. The most important endotracheal tube parameters that affect the vocal changes are the cuff mean pressure and volume. The laryngeal contribution to these vocal changes seems to be minimal. All vocal symptoms increased significantly except for globus pharyngeus at 2 hours postoperatively. The acoustic parameters did not change significantly except for a decrease in MPT. At 24 hours postoperatively, all vocal symptoms subsided with no significant difference to baseline value. The habitual pitch increased significantly, and the rest of the parameters remained comparable to baseline value.     

Roughness and turbulence intensity effects on the induced flow oscillation of a single cylinder

The effects of the surface roughness and the turbulence intensity on the dynamic characteristics of the flow induced oscillations of an elastically supported single circular cylinder in a cross flow in the vortex shedding and fluid elastic regions were experimentally investigated. The results of these experiments indicate that, for the vortex shedding region, increasing the surface roughness results in a reduction of the amplitude of oscillation, while in the fluid elastic region, increasing the surface roughness tends to enhance the oscillations. A similar trend for the dynamic response of the cylinder in the vortex shedding region was also observed when the free stream turbulence intensity was varied, while in the fluid elastic region variations in the free stream turbulence intensity were observed to have no drastic effect on the dynamic response of the cylinder.     

Rates of intra- and intermolecular electron transfers in hydrogenase deduced from steady-state activity measurements

Electrons are transferred over long distances along chains of FeS clusters in hydrogenases, mitochondrial complexes, and many other respiratory enzymes. It is usually presumed that electron transfer is fast in these systems, despite the fact that there has been no direct measurement of rates of FeS-to-FeS electron transfer in any respiratory enzyme. In this context, we propose and apply to NiFe hydrogenase an original strategy that consists of quantitatively interpreting the variations of steady-state activity that result from changing the nature of the FeS clusters which connect the active site to the redox partner, and/or the nature of the redox partner. Rates of intra- and intermolecular electron transfer are deduced from such large data sets. The mutation-induced variations of electron transfer rates cannot be explained by changes in intercenter distances and reduction potentials. This establishes that FeS-to-FeS rate constants are extremely sensitive to the nature and coordination of the centers.     

Theoretical study with vibration–rotation and dipole moment calculations of quartet states of the CrCl molecule

The potential energy curves have been investigated for the 10 lowest quartet electronic states in the ^2s+1Λ^± representation below 30,000 cm^?1 of the molecule CrCl via CASSCF and MRCI (singly and doubly excitation with Davidson correction) calculations. The harmonic frequency ω_e, the internuclear distance r_e, the rotational constant B_e, the electronic energy with respect to the ground state T_e, and the permanent dipole moment μ have been calculated. By using the canonical functions approach, the eigenvalues E_v, the rotational constant B_v, and the abscissas of the turning points r_min and r_max have been calculated for the considered electronic states up to the vibrational level v = 19. Seven electronic states have been studied here theoretically for the first time. The comparison of these values to the theoretical results available in the literature shows a good agreement. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Experimental analysis on vortex tube energy separation performance

The present study reports the effect of several operating parameters on the thermal performance of the vortex tube. The experimental results indicate that the inlet pressure and the cold fraction are the most significant parameters influencing the vortex tube performance. The experimental data point out that insulation has minimal effect on the vortex tube performance. The same inlet pressure tests show that energy separation increases as number of inlet nozzle increases.     

The influence of nonuniform coating and taylor dispersion on the evaluation of capillary column inverse gas chromatography

A mathematical model which takes into account the combined effect of Taylor dispersion and film eccentricity on the elution profiles has been developed for the analysis of a capillary column inverse gas chromatography (CCIGC) experiment. In this paper, we present an additional improvement on the model presented by Hamdan et al. [E. Hamdan, J. F. Milthorpe, J. C. S. Lai, J. Chromatogr. A, 1078 (2005) 144] to include the effect of coating nonuniformity. The new model shows that while Taylor dispersion effect has a very significant effect on the elution profiles at low values of beta and gamma, the general effect of film asymmetry is to reduce this effect. At sufficiently large gamma and/or beta values, Taylor dispersion effect becomes negligible and the elution profiles will be mainly affected by film asymmetry. The inclusion of Taylor dispersion effect will increase the variance of the elution curves which could significantly affect the estimated value of the diffusivity Dp. The error in the estimated Dp values obtained using the Pawlisch et al. [C. A. Pawlisch, J. R. Bric, R.L. Laurence, Macromolecules 21 (1988) 1685] nonuniform model increases as gamma and/or beta are reduced and when the coated polymer exhibits less deviation from uniform films.     

Photo-physical properties and amplified spontaneous emission of a new derivative of fluorescein

The synthesis of new high-performance dyes and the implementation of new ways of incorporating the organic molecules into the solid host matrices have produced a great deal of activity in the field of solid-state dye lasers. In this article, the new laser dye, 2-(6-allyl-3-oxo-3H-xanthen-9-yl)-benzoic acid ethyl ester [AXBE] has been synthesized, and its chemical structure was confirmed by ¹H NMR, ¹³C NMR, IR and elemental analysis. This new dye was covalently bonded with methyl methacrylate (MMA) and 2-hydroxy ethyl methacrylate (HEMA) copolymer backbone and evaluated as the active medium of the solid-state laser dye. Its optical properties were experimentally investigated. Amplified spontaneous emission (ASE) and photostability were studied by pumping the dye sample with 355 nm (8 ns) pulsed Nd-YAG laser.