Adsorptive stripping square-wave voltammetric behavior of insulin

The adsorptive stripping voltammetric behavior of bovine insulin has been studied by both differential pulse and square-wave techniques, leading to analytical methodologies for its determination in aqueous samples and pharmaceutical preparations. The application of a square-wave mode for the stripping of adsorbed bovine insulin has proved to be much more sensitive, yielding signals 20 times larger than those obtained by applying a differential pulse scan. The precision obtained for the voltammetric method, at a concentration level as low as 0.77 mg L^–1 of the protein, was found to be 1.45% (RSD., n = 8) by SWS and 2.20% (RSD., n = 8) by DPS. The pharmaceutical product Actrapid containing biosynthetic human insulin was analyzed by both methods. Received: 25 February 1999 / Revised: 6 April 1999 / Accepted: 12 April 1999     

Dynamics of excitations in molecular condensates

Generalized master equations describing an exciton (electron) system interacting with a phonon bath and an ultrashort quantum optical pulse are derived. They are considerably simpler than those derived earlier although they are able to describe the interplay of creation, annihilation, propagation and relaxation of an excitation in its full complexity. Their range of validity is limited to smaller values of the excitation and to a weaker exciton-phonon coupling. The work arised during author’s Ph.D. studies in Institute of Physics of Charles University, Faculty of Mathematics and Physics, Ke Karlovu 5, 121 16 Praha 2, Czech Republic.     

np → ηd near threshold and the s -wave ηN amplitude

We calculate the process np → ηd near threshold using a separable potential model of the coupled ηN - πN - ππN subystems, and a relativistic three-body calculation for the ηd scattering amplitude. The ππN channels are represented by an effective σN channel, and we compare the case where the σ and π masses are related by m _σ = 2m _π and no width is considered, to another where the mass and width of the σ -meson are taken from ππ scattering data. The np → ηd cross-section can be well described up to about 60MeV by models where the real part of the ηN scattering length lies between 0.4≤Re(a _ηN)≤0.6 fm which allows us to determine the s -wave ηN scattering amplitude for -60≤E≤60 MeV.     

Extended Hildebrand solubility approach applied to sulphadiazine,sulphamerazine and sulphamethazine in some {1-propanol (1) + water (2)} mixtures at 298.15 K

Extended Hildebrand solubility approach (EHSA) was applied in this research to analyse the equilibrium solubility of sulphadiazine, sulphamerazine and sulphamethazine in some {1-propanol (1) + water (2)} mixtures at 298.15 K. Reported experimental solubilities and some fusion properties of these drugs were used for EHSA calculations. A good predictive character of EHSA (with mean deviations lower than 4.0%) was found by using regular polynomials in order five when correlating the interaction parameter (W) and the Hildebrand solubility parameter of solvent mixtures free of drug (δ₁₊₂). Nevertheless, the predictive character of EHSA was almost the same as obtained when logarithmic drug solubilities (log x₃) were correlated with δ₁₊₂ by using a fifth-degree regular polynomial.     

Mass spectrometry of humic substances of different origin including those from Antarctica A comparative study

Mass spectra of humic acids (HA) from different sampling sites (Antarctica, Brazil, Czech Republic, Mexico and USA) and origin (plant, soil, peat, and coal derived) were obtained by laser desorption/ionization time of flight mass spectrometry (LDI-TOF MS). Optimisation of the experimental conditions are given as the optimal value of the laser energy at 20–30% higher than the threshold. Under these conditions, reproducible mass spectra of HA samples were obtained. In the mass spectra the majority of the peaks are observed in the m/z region 100–1000 Da. Mass spectra fingerprints of HA were analyzed and, in spite of the differences in their origin, a number of common features and profiles (patterns of peaks) were observed in most of the samples. Very similar structural groups (patterns) of the peaks are present in the m/z range 717–918 Da for HA samples of quite different origins, countries or continents.

The tandem LDI-TOF MS and multivariate statistical tools allowed us to extract and elucidate underlying information contained in the mass spectra of the HA samples under study. Applying principal components and cluster analysis, it was, e.g. demonstrated that most of the Antarctica HA samples show distinguishable differences when compared with humic acids from other continents and of different origin.     

A DFT study of the pericyclic/pseudopericyclic character of cycloaddition reactions of ethylene and formaldehyde to buta-1,3-dien-1-one and derivatives

Cycloaddition reactions of ethylene and formaldehyde to buta-1,3-dien-1-one and derivatives were studied by performing a density functional theory study with the 6-31+G* basis set. Reactants, products, and transition states for each reaction were localized, and the path connecting reactants and products was also obtained. Magnetic properties were evaluated along the reaction path to elucidate the characteristics of the reactions studied. Also, a natural bond orbital analysis was performed to study the orbital interactions in the transition states. Calculations indicate that all reactions are pericyclic except three cases, which are pseudopericyclic reactions. In the latter, transition states are almost planar, and magnetic properties do not reveal aromatization enhancement in their transition states. Also, though the participation of lone pairs diminish the pericyclic character of the reactions, sometimes this participation is not enough to generate a change to a pseudopericyclic path. Overall, magnetic properties reveal as a good criterion to elucidate the characteristics of the reactions studied, though a combined application of several criteria is recommended.