Hydrogen bonding in Schiff bases--NMR, structural and experimental charge density studies

A series of sixteen Schiff bases (derivatives of salicylaldehydes and aryl amines) was studied to reveal the influence of substituents and the length of the linker on the properties of the H-bonding formed. In theory, two groups of compounds, derivatives of 2-(2-hydroxybenzylidenoamine)phenol) and 2-hydroxy-N-(2-hydroxybenzylideno)benzylamine, can form different types of H-bonds using one or two hydroxyl groups present in the molecules. Two other groups of compounds, derivatives of 4-(2-hydroxybenzylidenoamine)phenol and N-(2-hydroxybenzyideno)benzylamine, can form only one type of H-bond. It was confirmed by (15)N and (13)C NMR experiments, that in all cases only traditional, H-bonded six-membered chelate rings were formed. The positions of the hydrogen atom in the rings depend on the substituent and phase. Generally, the OH H-bond form dominates in solution, with exception of the nitro derivatives, where the NH tautomer is present. In the solid state the tautomeric equilibrium is strongly shifted to the NH form. Only for the 5-Br derivative of one compound was the reverse relationship found. According to the results of experimental charge density investigations, two intramolecular H-bonds in the 5-methoxy derivative of 2-hydroxy-N-(2'-hydroxybenzylideno)benzylamine) differ significantly in terms of charge density properties. The intra- and intermolecular H-bonds formed by the deprotonated oxygen atom from 2-OH group are strong, with significant charge density concentration at the bond critical point and a straight, well-defined bond path, whereas the second intramolecular H-bond formed by the oxygen atom from the 2'-OH group is quite weak, with ca. five times smaller charge density concentration than in the previous case and a bent bond path. In terms of energy densities, the latter H-bond appears to be a non-bonding interaction, with total energy density being slightly positive. In terms of source contributions to the density at the H-bond critical point from the atoms involved, the intermolecular, linear H-bond is very strong and charge-assisted in the source function classification, the N(1)-H(1N)···O(1) H-bond is medium-strength, while the third H-bond is extremely weak.     

Low-temperature ordering effects in diblock copolymer melts from lattice simulation

A lattice simulation of a model diblock copolymer melt is presented. In a series of simulation experiments an 8-8 diblock melt is quenched from an athermal state to 47 lower temperatures. A set of simulation boxes, 30 x 32 x 30, 40 x 32 x 60, 50 x 32 x 30, and 60 x 32 x 30, is used in order to explore the size effects. Energy, specific heat, copolymer end-to-end distance, lamellar spacing, and the degree of interfacial ordering are reported. For all sizes considered, the low-temperature interfacial ordering is noticeable.     

Application of microextraction by packed sorbent to isolation of psychotropic drugs from human serum

A method of microextraction by packed sorbent (MEPS) followed by liquid chromatography with diode array detection has been developed and optimized for the extraction of six tricyclic antidepressants (amitriptyline, nortriptyline, imipramine, desipramine, doxepin, nordoxepin) from human serum. The optimal parameters of MEPS extraction (type of sorbent, volume of sample, composition, and volume of washing and elution solutions) for these drugs in spiked samples were defined. The developed MEPS procedure was validated and then successfully applied to the analysis of serum reference material. The limit of detection (0.02–0.05 μg/mL), intraday (2.7–8.8%) and interday (4.4–11.6%) precision (RSD), and the accuracy of the assay (94.5–108.8%) at three concentration levels—0.2, 0.5, and 0.8 μg/mL—were estimated. The accuracy of the method was evaluated by the analysis of certified reference material. Moreover, the validated procedure was compared with the solid-phase extraction technique. Finally, microextraction by packed sorbent was assessed as a suitable tool in forensic and clinical methods for serum sample preparations.     

On the microdynamics of composite plates

Summary The subject of the contribution is an investigation of elastic composite plates with a microperiodic structure along the plate's midsurface. The computational models of the plates are largely based on the homogenization procedures leading to equations with constant coefficients. However, the homogenization theories neglect the microstructure length-scale effect on the plate's dynamic behaviour. The objective of this research is to formulate and investigate a refined theory of the composite plates under consideration, which would describe the microdynamic plate behaviour caused by the microstructure. The possible applications of the proposed theory are shown by an example.This research was partly supported by KBN, Warsaw, under grant 3 3310 92 03.     

Determination of the absolute configurations using electronic and vibrational circular dichroism measurements and quantum chemical calculations

The stereochemistry of products obtained via a chemical reaction may not always be obvious from the reaction scheme utilized. The identification of convenient methods to determine the stereochemistry in such cases is highly desirable. To identify these methods, we considered a substituted 4-vinyl-1-azabicyclo[3.2.0]hept-3-en-7-one that undergoes spontaneous oxidation in the atmosphere at room temperature, yielding an epoxide with unknown absolute configuration. To determine the absolute configuration of the resulting epoxide, three different approaches have been utilized: (a) experimental NOE measurements; (b) experimental electronic circular dichroism (ECD) spectroscopic measurements and their analysis using corresponding quantum chemical predictions at the B3LYP/aug-cc-pVDZ level; (c) experimental vibrational circular dichroism (VCD) spectroscopic measurements and their analysis using corresponding quantum chemical predictions at the B3LYP/aug-cc-pVDZ level. It was found that the NOE data could not provide enough proof for assigning the absolute configuration, while ECD data could not provide enough discrimination to distinguish between the two possible stereoisomers. On the other hand, VCD spectroscopic analysis provided enough discrimination to distinguish between the two possible stereoisomers, and the absolute configuration could be assigned with confidence.     

Cross sections for nuclear reactions in collisions of238U+238U and238U +197Au near and below the coulomb barrier

Cross sections for nuclear reactions at beam energies near and below the spherical Coulomb barrier V _c were measured in the very heavy collision systems²³⁸U +²³⁸U and²³⁸U +¹⁹⁷Au. The most probable reaction channel with mass transfer is the one-neutron transfer. Its excitation function is understood in terms of Rutherford trajectories together with the quantal process of neutron tunnelling over large distances. In addition, the exchange of up to 15 nucleons is observed down to 0.90 V _c . The excitation functions for the multi-nucleon transfer products have much steeper slopes than that for one-neutron transfer, and are steeper for²³⁸U +¹⁹⁷Au than for²³⁸U +²³⁸U, suggesting that nuclear contact is established in the associated collisions. The angular distribution for one selected multi-nucleon transfer product,²²⁷Th, shows that its formation occurs in more central collisions within contact times shorter than about 10^?21 s. There is no evidence for very longlived di-nuclear systems in the these reactions.     

Crystal and magnetic structure of a novel compound UCu5Al. Structural stability with Th-substitution

The antiferromagnetically ordered, moderate heavy fermion UCu₅Al, crystallises in the original tetragonal I4/mmm structure, which remains unchanged in the U_1−xTh_xCu₅Al solid solutions up to x≈0.35. Above this composition, other solid solutions with general chemical formula (U_1−xTh_x)(Cu_1−yAl_y)₅ are formed, having a different type of structure, namely the hexagonal CaCu₅-type. Below T_N=18 K UCu₅Al orders with a sine-modulated, incommensurate magnetic structure described by a wave vector k=(0, 0, 0.55) and the moment amplitude of 1.45(5) μ_B at 1.4 K.     

Viscosity of glycerol solutions of Csl at several temperatures

The viscosities of Csl in glycerol were measured at 43, 60, and 80°C at concentrations up to about 0.2 mole-liter^–1. The Jones-Dole viscosityB coefficients were negative with a negative temperature coefficient. This is the first reported case of a negativeB coefficient with a negative temperature coefficient for any solvent system.     

Thermochemical investigation of NaI,CsI, and LiCl solutions in glycerol

Measurement of the dissolution enthalpies of NaI, CsI and LiCl in the 0.008–1.5 molar concentration range has been carried out using an “isoperibol” type calorimeter in the temperature range 316.15–363.15 K. The results of the thermochemical investigations suggest the ordering effect of the mentioned salts on the structure of glycerol.