Correlation in stimulated respiratory neural noise

Noise in spontaneous respiratory neural activity of the neonatal rat isolated brainstem-spinal cord preparation stimulated with acetylcholine (ACh) exhibits positive correlation. Neural activity from the C4 (phrenic) ventral spinal rootlet, integrated and corrected for slowly changing trend, is interpreted as a fractal record in time by rescaled range, relative dispersional, and power spectral analyses. The Hurst exponent H measured from time series of 64 consecutive signal levels recorded at 2 s intervals during perfusion of the preparation with artificial cerebrospinal fluid containing ACh at concentrations 62.5 to 1000 &mgr;M increases to a maximum of 0.875+/-0.087 (SD) at 250 &mgr;M ACh and decreases with higher ACh concentration. Corrections for bias in measurement of H were made using two different kinds of simulated fractional Gaussian noise. Within limits of experimental procedure and short data series, we conclude that in the presence of added ACh of concentration 250 to 500 &mgr;M, noise which occurs in spontaneous respiratory-related neural activity in the isolated brainstem-spinal cord preparation observed at uniform time intervals exhibits positive correlation. (c) 1995 American Institute of Physics.     

Schatten class composition operators on weighted Bergman spaces of bounded symmetric domains

Summary We obtain trace ideal criteria for 0A ² () of a Bounded symmetric diomain in _n.     

Four- and Five-Coordinate Oxovanadium(V) Alkoxides: Do Steric Effects or Electronic Properties Dictate the Geometry?

Sterically hindered ligands generally form metal complexes with lower coordination numbers than less hindered ligands. In contrast to dogma, the solid state vanadium(V) complexes with ethylene glycol and pinacol contain four- and five-coordinate vanadium atoms, respectively. Ab initio and electrostatic potential distribution calculations were conducted on both experimental and optimized geometries of the four- and five-coordinate oxovanadium chloroalkoxides. Ab initio energy calculations favor the five-coordinate species for all ligands at all levels of theory examined. No significant differences in the electrostatic properties of the vanadium atoms in the two types of molecules were observed by using electrostatic potential distribution analysis. Methyl group substitutions on the ligand did not change the electronics of the vanadium atoms sufficiently to be a factor. Thus, we conclude that neither electronics nor sterics at the metal center explains the experimental geometries. In the absence of a significant observable electronic effect at the vanadium, we note that the experimental observations can be attributed to ligand geometric effects such as the Thorpe-Ingold and/or gem-dialkyl effects.     

Cycloadditions dipolaires-1,3 II. Addition des diarylnitrilimines au N-methyl-indole. Etude expérimentale et essai d'interprétation

The reactivity of N-methylindole towards diarylnitrilimines has been studies. The cycloadducts are 8-methyl-3a,8a-dihydro-pyrazolo[3,4-b] indole derivatives. The structure reported was assigned on the bases of satisfactory analytical, spectroscopic and chemical data. An interpretation based on the second order perturbation method of frontier orbitals is in agreement with the observed regiospecificity.     

Molecular orbital calculations on the conformation of polypeptides and proteins

Quantum mechanical calculations using the PCILO method have been performed on the tripeptide model CH₃CO-X-Y-NHCH₃. Competition between C₅, C₇, C₁₀ rings and open structures has been investigated through mapping of the whole {φ, Ψ} conformational space and energy minimization. From these results, it appears that the C₁₀ ring simulating the folding named U-turn, involving a hydrogen bond between the i...i + 3 residues, is the most probable structure although not the most stable in energy. The results are used for predicting the frequency of U-turns in proteins, α-chymotrypsin is given as an example.     

Remarkable remote chiral recognition in a reaction mediated by a catalytic antibody

The crystal structures of catalytic antibody D2.3 Fab with the two enantiomers, 7D and 7L, which represent transition state analogues for the hydrolysis of the corresponding esters, 6D and 6L, were determined to better understand remarkable reactivity differences: the L-ester displayed significantly tighter binding (K(M)) and increased catalytic activity (k(cat)) with D2.3, even though the chiral center is 7 bonds distant from the reaction center. Surprisingly, the electron densities of the liganded phosphonates, 7D and 7L, within the D2.3 binding/reaction site were essentially identical, highlighting the subtle influences of protein interactions on chemical behavior.     

Rationale for kinetic heterogeneity of ultrafast light-induced electron transfer from Ru(II) complex sensitizers to nanocrystalline TiO2

Because of their successful use in dye-sensitized solar cells, Ru(II) polypyridyl complex dyes adsorbed on nanocrystalline TiO2 films have been regarded as model systems for the experimental study of the ultrafast dynamics of interfacial light-induced electron transfer. Most studies have reported charge injection kinetics from Ru(dcbpyH2)2(NCS)2 (N3) to take place with a fast (sub-100 fs) phase, followed by a slower (0.7-100 ps) multiexponential component. This complex, multiphasic behavior observed for the electron injection process has prevented the development of a satisfying kinetic model and has led to often contradicting conclusions. Here, we show that the observed kinetic heterogeneity can result from the aggregation of sensitizer molecules on the surface. Carefully controlled deposition of Ru(II) complex dye molecules onto nanocrystalline titania consistently yields a monophasic injection dynamics with a time constant shorter than 20 fs. The latter figure suggests the process is beyond the scope of vibration-mediated electron transfer kinetic models and might be controlled by the electron dephasing in the solid.     

Inframolecular protonation process of norbadione A: influence of the ionic environment and stereochemical consequences

The microscopic protonation mechanism, at an inframolecular level, of norbadione A, a pigment extracted from mushrooms and known to complex cesium cations, was determined by using 1H NMR titrations and the cluster expansion method. This study revealed a pH dependent Z to E isomer switch that occurs in both pulvinic moieties. As a consequence, norbadione A can exist in solution in four stereomeric forms (E-E, E-Z, Z-E, and Z-Z), which can be of interest in the development of molecular-level devices. In the presence of 0.15 M NaCl, the calculated microconstants showed an unusual apparent cooperativity between the enol groups, which results from the release of the sodium cations upon protonation of norbadione A.