Solution of solute transport in unsaturated porous media by the method of characteristics

A degenerate convection‐diffusion problem is approximated using the scheme that is based on the relaxation method and also the method of characteristics. A mathematical model for solute transport in unsaturated porous media is included. Moreover, multiple site adsorption is considered. Convergence of the scheme is proved and numerical experiments in 1D and 2D are presented. © 2003 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 19: 732–761, 2003.     

Investigation of chloromethane complexes of cryptophane‐A analogue with butoxy groups using 13C NMR in the solid state and solution along with single crystal X‐ray diffraction

Host‐guest complexes between cryptophane‐A analogue with butoxy groups (cryptophane‐But) and chloromethanes (chloroform, dichloromethane) were investigated in the solid state by means of magic‐angle spinning ¹³C NMR spectroscopy. The separated local fields method with ¹³C‐¹H dipolar recoupling was used to determine the residual dipolar coupling for the guest molecules encaged in the host cavity. In the case of chloroform guest, the residual dipolar interaction was estimated to be about 19 kHz, consistent with a strongly restricted mobility of the guest in the cavity, while no residual interaction was observed for encaged dichloromethane. In order to rationalize this unexpected result, we performed single crystal X‐ray diffraction studies, which confirmed that both guest molecules indeed were present inside the cryptophane cavity, with a certain level of disorder. To improve the insight in the dynamics, we performed a ¹³C NMR spin‐lattice relaxation study for the dichloromethane guest in solution. The system was characterized by chemical exchange, which was slow on the chemical shift time scale but fast with respect to the relaxation rates. Despite these disadvantageous conditions, we demonstrated that the data could be analyzed and that the results were consistent with an isotropic reorientation of dichloromethane within the cryptophane cavity. Copyright © 2015 The Authors. Magnetic Resonance in Chemistry published by John Wiley & Sons Ltd.     

Synthesis and crystal structure study of 2′-Se-adenosine-derivatized DNA

The selenium derivatization of nucleic acids is a novel and promising strategy for 3D structure determination of nucleic acids.Selenium can serve as an excellent anomalous scattering center to solve the phase problem,which is one of the two major bottlenecks in macromolecule X-ray crystallography.The other major bottleneck is crystallization.It has been demonstrated that the incorporated selenium functionality at the 2′-positions of the nucleosides and nucleotides is stable and does not cause significant st...     

New materials with high π conjugation by reaction of 2-oxazoline containing phenols with polyamidines and inorganic base

The non-covalent interactions between 2-oxazoline containing phenols and an aliphatic polyamidines as well as an inorganic base were studied. The reaction of a weak acid with a strong base results in the formation of the deprotonated species and subsequently in the formation of a new electronic structure. A bathochromic shift of the wavelength of the absorption maxima of the chromophores bounded to polyamidine was observed. Depending on the structure of the chromophore, the shift of the absorption maxima is 40-100 nm. The changes in photochemical behavior can be explained by the higher portion of quinoid structures in the conjugated π-system. The degree of deprotonation is dependent on the molar ratio of the chromophore and the polymeric base. Analogous results were obtained with an inorganic base.     

The Progress of Ageing of Lignin-containing Paper Induced by Light and its Relation to Chemiluminescence – Temperature Runs

Lignin-containing papers from different sources and of different age were irradiated by the visible light and the progress of the degradation reaction was followed by non-isothermal chemiluminescence method. Kinetic data obtained for papers degraded in oxygen were compared with double fold endurance test and carbonyl groups concentration. The effect of lignin on degradation of cellulose after deacidification treatment of the paper by methoxymagnesium methylcarbonate (MMMC) was ascertained and a mechanism of co-oxidation of lignin and cellulose in originally alkaline conditions was outlined.     

Cooperative motion in amorphous polymers; application to the study of free-radical migration in solids

A Monte Carlo method has been used for studying the effect of the motion of some submolecular structures on the migration of radical centres and on the free-radical decay and its dependence on density. Motions of crank, crankshaft, kink, and double kink type are considered. A cooperative type of motions is also taken into account. The results show that cooperative motions support diffusion of radical centres and thus also the free-radical decay but, at higher densities, the cooperation of motions is restricted. The density of the system, where the decay of radicals is followed, affects the rate of the decay, its increase causes radical decay retardation. This is in line with the high pressure effect, which also retards the radical decay rate.