Impact of O–Si–O bond angle fluctuations on the Si–O bond-breakage rate

We extend the McPherson model for the silicon–oxygen bond-breakage in a manner to capture the impact of the O–Si–O angle fluctuations (typical for amorphous SiO₂) on the breakage rate. In the McPherson model the transition of the Si ion from the 4-fold coordinated position to the 3-fold coordination is considered as rupture of the Si–O bond. We have studied the potential barrier (separating these saddle points) transformation induced by the O–Si–O bond angle variations and found that the secondary minimum occurs at a critical angle of about 107.75°. Since the Si ion “finds” the way corresponding to the highest breakage probability we used the two-dimensional downhill simplex method in order to find the direction of this maximal rate. It was shown that if the O–Si–O angle deviates from its nominal value 109.48° (typical for α-quartz) corresponding to the regular SiO₄ tetrahedron the symmetry aggravates and the secondary minimum is rotated. Calculated dependencies of the breakage rate on the electric field demonstrate the linear slope in the log–lin scale thus reflecting the linear reduction of the activation energy for the bond-breakage vs. field. The family of distribution functions for breakage rate calculated with a fixed step of field shows that the curves do not change their form and are shifted in parallel with the field. This tendency supports the thermo-chemical model for the bond-breakage also in the case of strongly fluctuating O–Si–O angles. As a consequence, dependencies of the mean value of the rate, its standard deviation and the nominal rate (calculated for the angle of 109.48°) have the same slope on a log–lin scale. The wide spread of the breakage rate is reflected by the high value of its standard deviation.     

Revisiting play elements and self-handicapping in play: A comparative ethogram of five Old World monkey species.

Play behavior has been viewed as a mixture of elements drawn from “serious” behavior, interspersed by ritualized play signals. Two other types of play behaviors have been overlooked: patterns that are dissimilar from any serious behavior and patterns with self-handicapping character, that is, those that put the animal into unnecessary disadvantageous positions or situations. Here the authors show that these 2 types of patterns can constitute a major part of play repertoire. From our own videorecordings and observations, we constructed play ethograms of 5 monkey species (Semnopithecus entellus, Erythrocebus patas, Chlorocebus pygerythrus, Cercopithecus neglectus, and Cercopithecus diana). The authors evaluated the self-handicapping character of each pattern and in Hanuman langurs also the (dis)similarity to serious behavior. Of the 74 patterns in the 5 species, 33 (45%) were judged to have a self-handicapping character. Of 48 patterns observed in langurs, 16 (33%) were totally dissimilar to any serious langur behavior known to us. The authors discuss the possibility that the different types of play elements may have different functions in play. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Metabolic differentiation of neuronal phenotypes by single-cell capillary electrophoresis-electrospray ionization-mass spectrometry

Single-cell mass spectrometry (MS) is a rapidly emerging field in metabolic investigations. The inherent chemical complexity of most biological samples poses analytical challenges when using MS platforms to measure sample content without prior chemical separation. Here, a single-cell capillary electrophoresis (CE) system was coupled with electrospray ionization (ESI) MS to enable the simultaneous measurement of a vast array of endogenous compounds in over 50 identified and isolated large neurons from the Aplysia californica central nervous system. More than 300 distinct ion signals (m/z values) were detected from a single neuron in the positive ion mode, 140 of which were selected for chemometric data analysis. Metabolic features were evaluated among six different neuron types (B1, B2, left pleural 1 (LPl1), metacerebral cell (MCC), R2, and R15) chosen for their various physiological functions. The results indicated chemical similarities among some neuron types (B1 to B2 and LPl1 to R2) and distinctive features for others (MCC and R15 cells). The quantitative nature of the MS platform allowed the comparison of metabolite levels for specific neurons. The CE-ESI-MS approach for examination of individual nanoliter-volume cells as described herein is readily adaptable to other volume-limited samples.     

Surface runoff on loess: an example of a commonly overlooked hazardous process from northeast Czech Republic

Bulletin of Engineering Geology and the Environment - Engineering structures in the geological environment of loess sediments face a number of problems. An emphasis is placed on the surface runoff...