UV photolysis products of propiolic acid in noble-gas solids

Photolysis (193 nm) of propiolic acid (HCCCOOH) was studied with Fourier transform infrared spectroscopy in noble-gas (Ar, Kr, and Xe) solid matrixes. The photolysis products were assigned using ab initio quantum chemistry calculations. The novel higher-energy conformer of propiolic acid was efficiently formed upon UV irradiation, and it decayed back to the ground-state conformer on a time scale of approximately 10 min by tunneling of the hydrogen atom through the torsional energy barrier. In addition, the photolysis produced a number of matrix-isolated 1:1 molecular complexes such as HCCH...CO2, HCCOH...CO, and H2O...C3O. The HCCH...CO2 complex dominated among the photolysis products, and the computations suggested a parallel geometry of this complex characterized by an interaction energy of -9.6 kJ/mol. The HCCOH...CO complex also formed efficiently, but its concentration was strongly limited by its light-induced decomposition. In this complex, the most probable geometry was found to feature the interaction of carbon monoxide with the OH group via the carbon atom, and the computational interaction energy was determined to be -18.3 kJ/mol. The formation of the strong H2O...C3O complex (interaction energy -21 kJ/mol) was less efficient, which might be due to the inefficiency of the involved radical reaction.     

Effect of Co-flowing Vapor during Vertical Falling-film Evaporation

A large number of industrial processes use falling-film evaporation to concentrate liquid products. This technology allows for small temperature differences during operation and is often significantly more energy efficient than other techniques. When processing dairy products, a reduction in the solvent fraction results in an increased product viscosity and may thus result in non-Newtonian features. The interaction between a co-flowing vapor that is produced during the evaporation process and the falling film is an important feature of the process. Few studies have accurately studied the effect of co-flow on evaporative falling films at high solid contents. In this work, an experimental study of the influence of co-flowing vapor on the heat transfer coefficient for a dairy product is presented as a function of both the solid content (from 10 to 50%) and the mass flow rate of the feed. The experimental set-up, consisting of a unique industrial pilot-scale evaporator, provides the possibility of obtaining results useful for realistic industrial conditions. An analytical approach that enables the simultaneous evaluation of heat transfer in every experimental condition, e.g., for Newtonian or non-Newtonian fluids and with or without co-flowing vapors, is presented.     

On Backward p(x)-Parabolic Equations for Image Enhancement

In this study, we investigate the backward p(x)-parabolic equation as a new methodology to enhance images. We propose a novel iterative regularization procedure for the backward p(x)-parabolic equation based on the nonlinear Landweber method for inverse problems. The proposed scheme can also be extended to the family of iterative regularization methods involving the nonlinear Landweber method. We also investigate the connection between the variable exponent p(x) in the proposed energy functional and the diffusivity function in the corresponding Euler-Lagrange equation. It is well known that the forward problems converges to a constant solution destroying the image. The purpose of the approach of the backward problems is twofold. First, solving the backward problem by a sequence of forward problems, we obtain a smooth image which is denoised. Second, by choosing the initial data properly, we try to reduce the blurriness of the image. The numerical results for denoising appear to give improvement over standard methods as shown by preliminary results.     

Analysis and Optimization of an Adaptive Selective-Repeat Scheme for Time-Varying Channels with Feedback Errors

In this article, an adaptive SR ARQ scheme is analyzed and optimized in a time-varying channel environment with unreliable feedback. Two-state Markov models are assumed for both the forward and the returnchannel.This enables the time behaviour of the entire system to be modelledby a Markov chain. To have an easy-to-implement scheme, we choose the smaller packet size to be half of the bigger one. Thus, there is only oneindependent design parameter related to packet size. The other two parametersare associated with channel sensing. The performance of the adaptive schemeis measured by its average throughput, which is upper-bounded by the throughput of the so-called ideal adaptive scheme. This upper bound is very useful in the optimization of the packet size and other design parameters. From the results, it can be concluded that the selection of the packet size is at least as critical as the optimization of the other parameters. The feedback errors degrade the throughput of the scheme, but their effect on the parameter optimization turns out to be almost negligible.     

Normal Vibrations of Water in 1:1 Complexes

IR spectra of water in 1:1 complexes (HOH…B) show a characteristic change of the vibration frequencies v₁, v₂ and v₃ for differently strong bases (B). The normal vibrations in different complexes are calculated from the frequencies and the force constants f_OH, f_α, f_OH,OH. The normal vibrations show that v₃ (1:1) becomes the “free” and v₁ (1:1) the “bonded” OH vibration. The degree of coupling in these systems can be deduced directly from the observed band separation. For a base like water the degree of coupling in 1:1 complexes is about 40%.     

Analytical gradients of a state average MCSCF state and a state average diagnostic

An efficient method for calculating the Lagrange multipliers and the analytical gradients of one state included in a state average MCSCF wave function is presented. It is demonstrated that the state average energy of an ‘equal-weight’ scheme is invariant to rotations within the state average subspace and that the corresponding rotations should be eliminated from the Lagrangian equations. Finally, a diagnostic is presented, which gauges the energy difference between a state defined by a state average calculation and the corresponding fully variational multi-configurational SCF state.     

Voltammetric Sensors and Sensor System Based on Gold Electrodes Modified with Polyarylenephthalides for Cysteine Recognition

Russian Journal of Electrochemistry - Voltammetric sensors and a sensor system based on gold electrodes modified with polyarylenephthalides (chlorinated polyphthalidylidene fluorene and...