Substituent control of hydrogen bonding in palladium(II)-pyrazole complexes

Inter- and intramolecular hydrogen bonding of an N-H group in pyrazole complexes was studied using ligands with two different groups at pyrazole C-3 and C-5. At C-5, groups such as methyl, i-propyl, phenyl, or tert-butyl were present. At C-3, side chains L-CH(2)- and L-CH(2)CH(2)- (L = thioether or phosphine) ensured formation of chelates to a cis-dichloropalladium(II) fragment through side-chain atom L and the pyrazole nitrogen closest to the side chain. The significance of the ligands is that by placing a ligating side chain on a ring carbon (C-3), rather than on a ring nitrogen, the ring nitrogen not bound to the metal and its attached proton are available for hydrogen bonding. As desired, seven chelate complexes examined by X-ray diffraction all showed intramolecular hydrogen bonding between the pyrazole N-H and a chloride ligand in the cis position. In addition, however, intermolecular hydrogen bonding could be controlled by the substituent at C-5: complexes with either a methyl at C-5 or no substituent there showed significant intermolecular hydrogen bonding interactions, which were completely avoided by placing a tert-butyl group at C-5. The acidity of two complexes in acetonitrile solutions was estimated to be closer to that of pyridinium ion than those of imidazolium or triethylammonium ions.     

Triazino-1,2,4-[4,5-a] indoles IV. Etude des triazinoindolethiones

The 1,2-dihy dro-1,2,4-triazino[4,5-a] indole-1-thiones 2 and 3 obtained by sulphurization of the 1,2-dihydro-1,2,4-triazino-[4,5-a] indol-1-ones 1 and 4 with phosphorus pentasulphide are intermediate products in the synthesis of 1,2,4-triazino[4,5-a]-indolc 10 and 4-methyl-1,2,4 omdp;e 19. The thiolactam-thiolactim tautomerism was studied using the ir and nmr spectra and allowed N. and S.substitutions. The methylation with dimethyl sulphate afforded mixtures of N. and S. methyl derivatives which were separated by chromatographic analysis and identified by |21|0H nmr and unequivocal synthesis.     

Interaction Between a Linearly Polarized Electromagnetic Plane and a Double Spherical Shell

An exact solution inside, outside, and within two arbitrary concentric spherical shells is presented for an impinging monochromatic linearly polarized electromagnetic wave. Specifically, the solution was found for a double-shell spherical acrylic plastic enclosure irradiated with 2450-MHz microwaves. The enclosure is used as an environmentally controlled exposure chamber for experimental animals during microwave irradiation. The analysis shows that an air foamed material, such as styrofoam, would be a better material than either Plexiglas or Teflon, provided it is sufficiently durable.     

Synthesis methods of array antenna excitation laws

Standard numerical optimization methods become very computational time consuming when dealing with synthesis of array antenna excitation laws, especially when number of elements exceeds a few tenths. Array antenna designer needs a fast and efficient synthesis tool, since the design phase implies several reoptimizations within the definition phase, in order to satisfy tradeoffs on antagonistic requirements : performances, size, cost,… We propose the use of an efficient, from the computational time point of view, and secured, from the convergence point of view, synthesis method illustrated by two examples. The optimized solution satisfies a sta-tionarity condition, which leads to steady solutions in frequency but also with regard to errors (manufacturing, …). Based on analytical calculus performed before any numerical resolution and together with the use of fast Fourier transform algorithms, this method leads to reduced optimization times (in the order of a minute) for arrays of some tenths up to some hundred feeds, computations being performed on a pc. Two theoretical applications are presented and for each of them a computed example is also shown; moreover possible extensions are considered.     

Almost block independence and bernoullicity of ℤ d -actions by automorphisms of compact abelian groups

Summary We prove that a ^d -action by automorphisms of a compact, abelian group is Bernoulli if and only if it has completely positive entropy. The key ingredients of the proof are the extension of certain notions of asymptotic block independence from -actions to ^d -action and their equivalence with Bernoullicity, and a surprisingly close link between one of these asymptotic block independence properties for ^d -actions by automorphisms of compact, abelian groups and the product formula for valuations on global fields.Oblatum 20-X-1994     

Conception of a CATV-based MAN

The objective of this paper is to propose an architecture for aCAble TeleVision (CATV) network, capable of supporting two-way transmission. This evolution is necessary for the survival of the CATV industry in an era of deregulation and of the development of the B-ISDN by the telecommunications companies. A communication transactional service is then considered and performance analysis is done under realistic assumptions.     

Dysrhythmias of the respiratory oscillator

Breathing is regulated by a central neural oscillator that produces rhythmic output to the respiratory muscles. Pathological disturbances in rhythm (dysrhythmias) are observed in the breathing pattern of children and adults with neurological and cardiopulmonary diseases. The mechanisms responsible for genesis of respiratory dysrhythmias are poorly understood. The present studies take a novel approach to this problem. The basic postulate is that the rhythm of the respiratory oscillator can be altered by a variety of stimuli. When the oscillator recovers its rhythm after such perturbations, its phase may be reset relative to the original rhythm. The amount of phase resetting is dependent upon stimulus parameters and the level of respiratory drive. The long-range hypothesis is that respiratory dysrhythmias can be induced by stimuli that impinge upon or arise within the respiratory oscillator with certain combinations of strength and timing relative to the respiratory cycle. Animal studies were performed in anesthetized or decerebrate preparations. Neural respiratory rhythmicity is represented by phrenic nerve activity, allowing use of open-loop experimental conditions which avoid negative chemical feedback associated with changes in ventilation.In animal experiments, respiratory dysrhythmias can be induced by stimuli having specific combinations of strength and timing. Newborn animals readily exhibit spontaneous dysrhythmias which become more prominent at lower respiratory drives. In human subjects, swallowing was studied as a physiological perturbation of respiratory rhythm, causing a pattern of phase resetting that is characterized topologically as type 0. Computational studies of the Bonhoeffer-van der Pol (BvP) equations, whose qualitative behavior is representative of many excitable systems, supports a unified interpretation of these experimental findings. Rhythmicity is observed when the BvP model exhibits recurrent periods of excitation alternating with refractory periods. The same system can be perturbed to a state in which amplitude of oscillation is attenuated or abolished. We have characterized critical perturbations which induce transitions between these two states, giving rise to patterns of dysrhythmic activity that are similar to those seen in the experiments. We illustrate the importance of noise in initiation and termination of rhythm, comparable to normal respiratory rhythm intermixed with spontaneous dysrhythmias. In the BvP system the incidence and duration of dysrhythmia is shown to be strongly influenced by the level of noise. These studies should lead to greater understanding of rhythmicity and integrative responses of the respiratory control system, and provide insight into disturbances in control mechanisms that cause apnea and aspiration in clinical disease states. (c) 1995 American Institute of Physics.     

Composition of kinetic momenta: The(sl(2)) casecase

The tensor products of (restricted and unrestricted) finite dimensional irreducible representations of(sl(2)) are considered forq a root of unity. They are decomposed into direct sums of irreducible and/or indecomposable representations.