Analysis of dissolution profiles of iron,zinc, and manganese from complex dietary supplements by ion chromatography and chemometrics

Four commercially available formulations containing iron, zinc, and manganese were subjected to dissolution profile testing during 60 min and the dissolution was analyzed by ion chromatography. The obtained curves were analyzed directly by principal component analysis (PCA). The main trend (87.1% of variance) was connected with average dissolution percentage over the investigated time. The second component (11.2% of variance) is connected with shape of dissolution profile. All metals behave in the similar way and the differences were connected with excipients. An additional fit was completed on 12 kinetic models: first order kinetics (4 variants), Higuchi (2 variants), Hixson-Crowell (2 variants), Korsemeyer-Peppas, Logistic (2 variants), Peppas-Sahlin, Quadratic (2 variants), Weibull (3 variants), and Zero order kinetics (2 variants). The ranking of the fitting was performed by Akaike information criteria (AIC) values with additional PCA analysis on them, an approach presented in literature for the first time. The main trend (67.4% of variance) was connected with average fit. The second (14.8% of variance) is connected with differences of fitting ability to investigated dissolution curves. This methodology brought an overall look to trends and variances inside obtained data, both the profile shape and fitting ability to particular models.     

C-13 and H-1 NMR Study of Alkyl and Aryl-Substituted 1-(4′-Dimethylaminobenzylideneamino)pyridinium Perchlorates

C-13 and H-1 NMR spectra of some 1-(4′-dimethylaminobenzylideneamino)pyridinium perchlorates show that the angle of twist of the pyridine ring in unsubstituted, 1, and 2-alkyl substituted compounds 2–5 is comparable. However, it is considerably increased in 2,6-dialkyl derivatives. As seen from the spectral data, pyridine and phenyl rings in 2,6-diphenyl derivative 15 are not coplanar. The effect of 4-alkyl substituent is of hyperconjugative chacter. In general, the amount of the positive charge at C-4 in 2,6-dialkyl substituted salts is higher as compared to 2-monosubstituted compounds.     

A versatile entropic measure of grey level inhomogeneity

An entropic measure for the analysis of grey level inhomogeneity (GLI) is proposed as a function of length scale. It allows us to quantify the statistical dissimilarity of the actual macrostate and the maximizing entropy of the reference one. The maximums (minimums) of the measure indicate those scales at which higher (lower) average grey level inhomogeneity appears compared to neighbour scales. Even a deeply hidden statistical grey level periodicity can be detected by the equally distant minimums of the measure. The striking effect of multiple intersecting curves (MICs) of the measure has been revealed for pairs of simulated patterns, which differ in shades of grey or symmetry properties only. In turn, for evolving photosphere granulation patterns, the stability in time of the first peak position has been found. Interestingly, the third peak is dominant at initial steps of the evolution. This indicates a temporary grouping of granules at a length scale that may belong to the mesogranulation phenomenon. This behaviour has similarities with that reported by Consolini, Berrilli et al. [G. Consolini, F. Berrilli, A. Florio, E. Pietropaolo, L.A. Smaldone, Astron. Astrophys. 402 (2003) 1115; F. Berrilli, D. Del Moro, S. Russo, G. Consolini, Th. Straus, Astrophys. J. 632 (2005) 677] for binarized granulation images of a different data set.     

Enzyme mediated kinetic resolution of δ-hydroxy-α,β-unsaturated esters as a route to optically active δ-lactones

A novel synthetic route to optically active saturated and unsaturated δ-lactones based on enzymatic kinetic resolution and ring-closing metathesis reactions has been proposed. The influence of temperature, co-solvent, organic additives and the substrate structure on the catalytic behavior of selected hydrolases was studied. The substantial impact of the organic co-solvent and surfactant type on the enzymatic activity and enantioselectivity was observed providing enantiomerically pure δ-hydroxy-α,β-unsaturated esters. The established protocol combining enzymatic kinetic resolution with ring closing metathesis was successfully applied in the synthesis of the enantiomerically pure (6R)-phenyl-5,6-dihydro-2H-pyran-2-one which plays crucial role in the synthesis of the number of bioactive compounds.     

Speciation of seleno compounds in yeast aqueous extracts by three-dimensional liquid chromatography with inductively coupled plasma mass spectrometric and electrospray mass spectrometric detection

A three-dimensional liquid chromatographic purification protocol based on sequential size-exclusion, anion-exchange and cation-exchange separation mechanisms was developed for the mapping of seleno compounds in aqueous yeast extracts. The method allowed the demonstration of the presence of more than 30 different seleno compounds. Semi-preparative size-exclusion and anion-exchange chromatography were optimized for maximum resolution using electrospray-compatible buffers in order to purify the compounds for mass spectrometric analysis. Molecular masses were attributed to many of the compounds on the basis of the selenium isotopic pattern in the electrospray mass spectra and of the collision-induced fragmentation patterns. Limitations preventing the ultimate identification of the selenium species detected are discussed.     

Crystal structure of RbOsO3N: A new CsReO4-type compound

Crystals of RbOsO₃N are orthorhombic, space group Pnma, with z = 4, a = 5.571(1), b = 5.794(1), c = 13.735(3), Å. Intensities for 556 independent reflections collected on a four-circle diffractometer were used in the structure determination and the structure was refined to a final R value = 0.046 (R_w = 0.056). The structure consists of OsO₃N discrete tetrahedra linked together by 8-coordinated Rb ions. The oxygen and nitrogen atoms are distributed randomly. RbOsO₃N is the first compound belonging to the CsReO₄-type family for which the complete structure has been determined. This structure can be related to scheelite type but appreciable differences occur in tetrahedra arrangement.     

Polymerization of furil in the solid state by reaction with AsF5 at the solid–gas interface

Solid-state polymerization of furil, induced by reaction with AsF₅ at the solid–gas interface, has been investigated by means of vibrational analysis of the reactant and the product. Infrared spectra are consistent with the mode of Polymerization which involves an α,α′ linkage and subsequent loss of hydrogen atoms. The C/H elemental analysis suggests that the polymer consists of around six or seven monomeric units. The reaction product is found to be unstable at high temperatures; a prolonged annealing at this temperature leads to a different structure, possibly, by the opening of the furan rings. The x-ray powder diffraction study shows that the polymeric furil is crystalline, with a lattice similar to that of the monomer, but contains a considerable amount of disorder.     

Determination of T1-spin-lattice relaxation time in a two-level system by continuous wave multiquantum electron paramagnetic resonance spectroscopy in a presence of tetrachromatic microwave irradiation

Applicability of continuous wave multiquantum EPR methods to study relaxation times at X-band is examined. Multiquantum transitions excited in a two-level system by tetrachromatic irradiation are used for these studies. The Bloch equation model is applied to simulate lineshapes of the three quantum transitions as a function of frequency difference between exciting fields. The dependence of multiquantum transition signals on relaxation times and microwave amplitude is shown. On this basis a method of deducing relaxation times from these signals is formulated. The case of a homogeneously and inhomogeneously broadened resonance line is considered. Two experimental methods are used to verify the proposed hypothesis: the X-band continuous wave multiquantum EPR with four frequencies microwave field and saturation recovery EPR. The values of T₁ obtained from CW MQ EPR and SR EPR are compared.