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.     

Neutral Nickel(II) and Copper(II) Tetraazamacrocyclic Complexes as Molecular Rods Attached to Gold Electrodes

New dithiolated derivatives of neutral Cu^II and Ni^II tetraazamacrocyclic complexes have been synthesized and characterized by spectroscopic and diffractional methods. These rod‐shaped molecules were assembled in monocomponent and mixed monolayers on gold electrodes. In the mixed monolayers, the active molecules were embedded in a hexanethiol matrix. The dithiolated complexes are oriented perpendicularly to the electrode, and reveal faster kinetics of electron transfer than those assembled in a single‐component monolayer. They appear as protrusions, which are easily addressed by using the STM method. In the presence of a suitable electron acceptor in the solution, the donor properties of the anchored Cu complex were weakened, which revealed donor–acceptor interactions with the monolayer. The peak position in the voltammogram indicates a stronger interaction of the solution‐based acceptor with the reduced Cu^II form than with the Cu^III complex. This suggests the possibility of switching the association on or off by applying an appropriate potential.     

Double passage of electromagnetic waves through magnetized plasma: approximation of independent normal waves

Polarization properties of electromagnetic waves, double-passed through magnetized plasma, are studied. Analyses are performed in the case of non-interacting normal modes, propagating in homogeneous and weakly inhomogeneous plasmas, and for three kinds of reflectors: metallic plane, 2D corner retro-reflector (2D-CR), and cubic corner retro-reflector (CCR). It is shown that an electromagnetic wave, reflected from a metallic plane and from a CCR, contains only “velocity-preserving” channels, whose phases are doubled in comparison with those of a single-passage propagation. At the same time, an electromagnetic wave reflected from a 2D-CR is shown to contain both “velocity-preserving” and “velocity-converting” channels, the latter converting the fast wave into the slow one and vice-versa. One characteristic feature of “velocity-converting” channels is that they reproduce the initial polarization state near the source, which might be of practical interest for plasma interferometry. In the case of circularly polarized modes, “velocity-preserving” channels completely disappear, and only “velocity-converting” channels are to be found.     

Applying the Zigbee technology for the enhancing the remote objects control

The paper presents the monitoring and measurement processes for the remote object vibration in the plain space. Wireless, RF communication in Tx/Rx duplex mode provides transfer of data with ZigBee transceivers. Presented ZigBee technology operates in many various modes on frequency 2.4 GHz allowing the coordinator node to select certain path and data. ZigBee technology can be alternative for other vibration research techniques. The vibration displacement is processed further by DSP Digital Signal Processing, made with the microcontroller. Accelerometer applications due to embedded control and I/O digital signal processor DSP play the crucial role in determining vibration and machines fatigue strength testing. It registers, among other, the temporary industrial parameters and monitors plant system parameters such as vibration and/or pressure. The paper presents diagnostic procedure and measurements process of the vibration in the plain space. Role of the node play ZigBee transceivers. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure and interactions in homopolymers and blends as studied by the methods of vibrational and nmr spectroscopy

The combination of IR, Raman and NMR spectroscopy was used in the study of the blends of semicrystalline and amorphous polymers with considerably different strength of intermolecular interactions: poly(ϵ-caprolactam)/polystyrene (PCL/PS), poly(ethylene oxide)/poly(methyl methacrylate) (PEO/PMMA) and poly(N-methyllaurolactam)/poly(4-vinylphenol) (PNMLL/PVPh). In the vibrational and NMR spectra of the blends composed of non-interacting polymers (PCL/PS) and weakly interacting polymers (PEO/PMMA), no band changes were observed which would indicate changes of the conformational structures. ¹H NMR relaxation of the PCL and PS components in the blends is the same as in the respective homopolymers similarly treated. In the blends of weakly interacting polymers (PEO/PMMA), the crystallinity of PEO is influenced by the presence of PMMA and is negligible in the blends with less than 30 wt.-% of PEO. The rotating-frame spin-lattice relaxation time for protons T^H_1p of PMMA indicates close contact of the PMMA and PEO chains. In the blends PNMLL/PVPh with strong hydrogen-bonding interactions, both components are intimately mixed on a scale of 3–4 nm and significant shifts of some bands both in vibrational and in NMR spectra reveal changes of structure.     

Ergodicity of the 2-D Navier-Stokes equation under random perturbations

A 2-dimensional Navier-Stokes equation perturbed by a sufficiently distributed white noise is considered. Existence of invariant measures is known from previous works. The aim is to prove uniqueness of the invariant measures, strong law of large numbers, and convergence to equilibrium.