A simple and selective kinetic spectrophotometric method for the determination of kanamycin using acetylacetone-formaldehyde reagent in N,N′-dimethylformamide medium

A simple, sensitive, and selective kinetic spectrophotometric method for the determination of kanamycin in pure form and pharmaceutical formulations is described. The method is based on the measurement of the intensity of the yellow chromogen formed by the reaction between kanamycin and acetylacetone-formaldehyde reagent in a N,N′-dimethyl formamide medium. The variable-time method was used to evaluate the rate of reaction of the colored chromogen formed at 410 nm. The reaction conditions were optimized and the calibration graph was found to be linear in the range 60–160 μg/mL. The results obtained by the developed and reference methods are in good agreement. Various statistical parameters were evaluated to establish the precision, accuracy, repeatability, and reproducibility of the proposed method. The text was submitted by the authors in English.     

Delocalized electronic excitations of pentacene dimers in a p-terphenyl host: picosecond photon echo experiments

Photon echo experiments are performed on delocalized electronic excitations of optical dimer states. The delocalized dimer states are found to have very long coherence times, close to the coherent limit The dimer dephasing is qualitatively similar to dephasing of pentacene monomers.     

Ultrafast dynamics of myoglobin without the distal histidine: stimulated vibrational echo experiments and molecular dynamics simulations

Ultrafast protein dynamics of the CO adduct of a myoglobin mutant with the polar distal histidine replaced by a nonpolar valine (H64V) have been investigated by spectrally resolved infrared stimulated vibrational echo experiments and molecular dynamics (MD) simulations. In aqueous solution at room temperature, the vibrational dephasing rate of CO in the mutant is reduced by approximately 50% relative to the native protein. This finding confirms that the dephasing of the CO vibration in the native protein is sensitive to the interaction between the ligand and the distal histidine. The stimulated vibrational echo observable is calculated from MD simulations of H64V within a model in which vibrational dephasing is driven by electrostatic forces. In agreement with experiment, calculated vibrational echoes show slower dephasing for the mutant than for the native protein. However, vibrational echoes calculated for H64V do not show the quantitative agreement with measurements demonstrated previously for the native protein.     

Water dynamics and proton transfer in nafion fuel cell membranes

The dynamics of water and its effect on proton transport kinetics in Nafion membranes are compared at several hydration levels. Nafion is the most widely used polyelectrolyte membrane in fuel cells. Ultrafast infrared spectroscopy of the O-D stretch of dilute HOD in H2O provides a probe of the local environment and hydrogen bond network dynamics of water confined in the hydrophilic regions of Nafion. The kinetics of proton transfer in Nafion are tracked by following the excited-state proton transfer and recombination kinetics of a molecular probe, pyranine (HPTS). The hydrophilic domains of Nafion grow with increased hydration, and the interfacial regions reorganize, leading to a changing local environment for water near the interface. Swelling is not uniform throughout the membrane, and heterogeneity is observed in the fluorescence anisotropy decays of the methoxy derivative of pyranine. Measurements of the time-dependent anisotropy of water in Nafion provide a direct probe of the hydrogen bond network dynamics. These dynamics, as well as the rate of proton transport over nanoscopic distances, are observed to slow significantly as the hydration level of the membrane decreases. The results provide insights into the influence of changes in the dynamics of water on the proton-transfer processes.     

Accidental vibrational degeneracy in vibrational excited states observed with ultrafast two-dimensional IR vibrational echo spectroscopy

The coupling between the OD stretch v=2 level and benzene-ring modes in 2-methoxyphenol-OD (hydroxyl H replaced by D) is observed with ultrafast two-dimensional (2D) IR vibrational echo spectroscopy. Because of this coupling, the 1-2 transition peak in the 2D spectrum is split into a doublet with peaks of approximately equal amplitudes. Several molecules and solvents were used to study this phenomenon. Near-IR (NIR) spectroscopy measurements and density-functional theory calculations (B3LYP6-31+G(d,p) level) were also applied. Experimental results and calculations show that the OD stretch 1-2 transition is coupled to a combination band related to the benzene-ring motions. A simple quantum-mechanical model indicates that the combination band has a frequency of 5172 and 5176.5 cm(-1) in CCl4 and hexane, respectively. The transition between this combination band and the ground state is too weak to detect by NIR. The transition between this band and the OD stretch first excited state is also so weak that most of the intensity of the doublet comes from the oscillator strength produced by coupling to the OD stretch. The model gives the coupling strengths as 6.5 and 7 cm(-1) in CCl4 and hexane, respectively.     

Surface ligands in the imprinting and binding of molecularly imprinted cross-linked micelles

Molecular recognition in water is challenging but water-soluble molecularly imprinted nanoparticle (MINP) receptors were produced readily by double cross-linking of surfactant micelles in the presence of suitable template molecules. When the micellar surface was decorated with different polyhydroxylated ligands, significant interactions could be introduced between the surface ligands and the template. Flexible surface ligands worked better than rigid ones to interact with the polar moiety of the template, especially for those template molecules whose water-exposed surface is not properly solvated by water. The importance of these hydrophilic interactions was examined in the context of different substrates, density of the surface ligands, and surface-cross-linking density of the MINP. Together with the hydrophobic interactions in the core, the surface hydrophilic interactions can be used to enhance the binding of guest molecules in water.     

Shortest Path Problem on a Network with Imprecise Edge Weight

A network with its arc lengths as imprecise number, instead of a real number, namely, interval number and triangular fuzzy number is considered here. Existing ideas on addition and comparison between two imprecise numbers of same type are introduced. To obtain a fuzzy shortest path from a source vertex to all other vertices, a common algorithm is developed which works well on both types of imprecise numbers under consideration. In the proposed algorithm, a decision-maker is to negotiate with the obtained fuzzy shortest paths according to his/her view only when the means are same but the widths are different of the obtained paths. Otherwise, a fuzzy optimal path is obtained to which the decision-maker always satisfies with different grades of satisfaction. All pairs fuzzy shortest paths can be found by repeated use of the proposed algorithm.