Buffer composition changes in background electrolyte during electrophoretic run in capillary zone electrophoresis

The electrophoretic behaviors of different analytes in capillary zone electrophoresis were studied by the Whole Column Imaging Detection (WCID). For capillary zone electrophoresis (CZE) in conventional buffer systems, non-constant sample plug movement characterized by progressive decrease of peak migration velocity was observed. The appropriate velocity decrease was correlated with a degree of ionization of the analyzed ion, thus the effect observed could be explained by fast buffer composition change resulting in the development of a non-linear pH gradient. To visualize the appropriate pH gradient, the concentration profile of initially uniformly distributed amphoteric substances was also monitored. The evolution of the concentration profile exhibited very complex dynamics. In addition, it was found that the nature of the electrode solutions strongly affect changes in the background electrolyte. In the case of traditional background electrolytes with an acid-base pair for electrode solutions a non-uniform ampholyte concentration developed quickly, leading finally to a quasi-stationary profile similar to those typical of IEF. Possible approaches to suppress a negative impact of the background electrolyte composition changes during electrophoretic run on CE-separation are presented herein. In particular it was observed that zwitterionic buffers are able to withstand prolonged electrolysis much better compared to traditional buffers.     

Photophysical, spectroscopic, and computational studies of a series of Re(I) tricarbonyl complexes containing 2,6-dimethylphenylisocyanide and 5- and 6-derivatized phenanthroline ligands

The ligand 2,6-dimethylphenylisocyanide (CNx) forms six complexes of the formula [Re(CO)3(CNx)(L)]+, where L = 1,10-phenanthroline (1), 5-chloro-1,10-phenanthroline (2), 5-nitro-1,10-phenanthroline (3), 5-methyl-1,10-phenanthroline (4), 5,6-dimethyl-1,10-phenanthroline (5), and 1,10-phenanthrolinopyrrole (6). The lowest-energy absorption peaks of the complexes red-shift in the order 1 < 2 < 3 < 4 < 5 < 6. The time-dependent density functional theory (TDDFT) and conductor-like polarizable continuum model (CPCM) computed singlet excited states in ethanol deviate by 1000 cm(-1) or less from the experimental UV-vis peaks. The complexes undergo reversible reductions and irreversible oxidations. The electronic energy gap increases in the order 3 < 2 < 1 < 4 < 5 < 6, which is the order of increasing electron-donating power of the phen substituents. The reduction potentials linearly correlate with the B3LYP calculated LUMO energies for 1-6. The complexes emit at room temperature and at 77 K except 3, which emits only at 77 K. The calculated (3)MLLCT energies are within 1100 cm(-1) from the experimental emission energies at 77 K. The 77 K emission curve-fitting analysis results agree with the computational assignment of the emitting state as 3MLLCT for 1-5 and 3LC for 6. The experimental 77 K emission energies and the calculated 3MLLCT state energies increase in the order 6 < 5, 3 < 2 < 4, 1. The 77 K emission lifetimes increase upon addition of substituents from 65 micros for 1 to 171 micros for 2, to 230 micros for 4 and 5, and to 322 micros for 3. The emission quantum yields at room temperature in solution are 0.77, 0.78, 0.83, 0.56, and 0.11 for complexes 1, 2, 4, 5, and 6, respectively.     

Informationsgehalt chemischer Elemente

The information approach for describing electronic structures of atoms was developed and different information characteristics of chemical elements were determined on this basis. The information functions display interesting features and correlate with the properties of chemical elements. The spin information of the elements having a closed electron shell, expressed in bits, was found to be equal to the atomic number of the element.

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Mit 8 Abbildungen     

A study of an elastomeric coating based on EPDM of cold vulcanization

Studies of the thermostability of vulcanizates of ethylene–propylene–diene rubbers (EPDM) obtained by using dinitrosogenerating systems of low-temperature vulcanization are performed. It is shown that vulcanizates retain sufficient high properties in operation up to 200°C for a long time. The use of such compositions for producing thin rubber coatings applied on a number of insulating materials allows the effect of energy saving to be obtained.     

The effect of an amino-containing modifier on properties of ethylene copolymers

The effect of some aminosilanes on the complex of properties of ethylene copolymers with vinylacetate, acrylates, and ternary ethylene copolymers with vinylacetate or acrylates and maleic anhydride is studied.     

Filippov–Pliss lemma and m-dissipative differential inclusions

In the paper we prove a variant of the well known Filippov–Pliss lemma for evolution inclusions given by multivalued perturbations of m-dissipative differential equations in Banach spaces with uniformly convex dual. The perturbations are assumed to be almost upper hemicontinuous with convex weakly compact values and to satisfy one-sided Peron condition. The result is then applied to prove the connectedness of the solution set of evolution inclusions without compactness and afterward the existence of attractor of autonomous evolution inclusion when the perturbations are one-sided Lipschitz with negative constant.     

Structure of binary mixtures of ethylene-vinylacetate copolymers

The method of differential scanning calorimetry was used to analyze the structure of binary mixtures of ethylene and vinylacetate copolymers with different contents of reagent monomers. The anomalous deviation of the degree of crystallinity from additivity in the system is found and a possible interpretation of this experimental fact is suggested.