Metalloporphyrins in Oxidative Catalysis. Oxygen Transfer Reactions of Oxochromium Porphyrins

The oxidation of chloro-5-10,15,20-tetramesitylporphyrinotoiron(III) with peroxyacids affords a reactive oxoiron(IV)-porphyrin cation radical species 2. The characterization of 2 and its oxochromium analogs 3, 4 and 5 are reviewed. The nature of reactive oxochromium species derived from chromyl reagents is also reviewed. The oxidation of triphenylphosphine by CrOTPP (11), CrOTTP (13) and CrOTMP (14) is described. Variations in the rate constants indicate that steric factors affect the rate of oxygen atom transfer. Activation parameters for the oxidation of triphenylphosphine by 14 are ΔH^≠ = 6.96 kcal/mol and ΔS^≠ = −39 eu. The oxidation of t-butylphenylcarbinol (18) by CrOTPP gave predominantly benzaldehyde via carbon—carbon bond cleavage while the chromium(III) porphyrin-catalyzed oxidation of 18 by iodosylbenzene afforded t-butylphenylketone.     

Improved Matrix-Filler Adhesion

Enhanced matrix-filler adhesion is realized after filler treatment with a surface treatment process. The hydrosol/coupling agent treatment was applied to a wide range of inorganic and organic fillers, and adhesion to a variety of matrix resins was improved. Scanning Electron Microscopy (SEM) was used to determine the locus of failure in the filled systems. The locus of failure shows the relative degree of adhesion between the filler and the polymer matrix. Significant improvement in adhesion in humid environments is also observed.     

Hippocampal lesions impair memory of short-delay conditioned eye blink in rabbits.

Involvement of hippocampus in short-delay eye blink conditioning was reexamined during conditioned response (CR) consolidation. Rabbits received bilateral hippocampectomy, removal of overlying neocortex, or sham lesions and were trained with tone/puff pairings to early acquisition (consolidation) or well trained (overtraining); retention was tested. Two effects were observed: (1) Rabbits with hippocampal lesions showed less retention in the consolidation experiment than controls. Previous studies may not have found this because initial training was more complete. Overtrained hippocampal rabbits showed more retention, which agrees with this suggestion. (2) Hippocampectomized rabbits showed larger CR amplitudes in the overtraining experiment. The complementary roles of hippocampus in the consolidation process during early learning and in modulating the expression of the amplitude/time course of behavioral CRs after associations are well learned are discussed. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Artificial neural network medical decision support tool: predicting transfusion requirements of ER patients.

Blood product transfusion is a financial concern for hospitals and patients. Efficient utilization of this dwindling resource is a critical problem if hospitals are to maximize patient care while minimizing costs. Traditional statistical models do not perform well in this domain. An additional concern is the speed with which transfusion decisions and planning can be made. Rapid assessment in the emergency room (ER) necessarily limits the amount of usable information available (with respect to independent variables available). This study evaluates the efficacy of using artificial neural networks (ANNs) to predict the transfusion requirements of trauma patients using readily available information. A total of 1016 patient records are used to train and test a backpropagation neural network for predicting the transfusion requirements of these patients during the first 2, 2-6, and 6-24 h, and for total transfusions. Sensitivity and specificity analysis are used along with the mean absolute difference between blood units predicted and units transfused to demonstrate that ANNs can accurately predict most ER patient transfusion requirements, while only using information available at the time of entry into the ER.     

Exceptions that prove the rule--Using a theory of motivated social cognition to account for ideological incongruities and political anomalies: Reply to Greenberg and Jonas (2003).

A meta-analysis by J. T. Jost, J. Glaser, A. W. Kruglanski, and F. J. Sulloway (2003) concluded that political conservatism is partially motivated by the management of uncertainty and threat. In this reply to J. Greenberg and E. Jonas (2003), conceptual issues are clarified, numerous political anomalies are explained, and alleged counterexamples are incorporated with a dynamic model that takes into account differences between "young" and "old" movements. Studies directly pitting the rigidity-of-the-right hypothesis against the ideological extremity hypothesis demonstrate strong support for the former. Medium to large effect sizes describe relations between political conservatism and dogmatism and intolerance of ambiguity; lack of openness to experience; uncertainty avoidance; personal needs for order, structure, and closure; fear of death; and system threat. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Oxygen content of the fixative is important in the interpretation of the ultrastructure of ischaemic myocardium

Isolated rat hearts were subjected to 15, 45, or 60 minutes of global ischaemia and then fixed by perfusion at 37°C with glutaraldehyde containing various amounts of oxygen. This either had been bubbled with 100% oxygen (PO₂ 620 mm Hg) or with 100% nitrogen (PO₂ 40 mm Hg) immediately before use, or it had been routinely prepared and stored exposed to atmospheric oxygen (PO₂ 245 mm Hg). The ultrastructure of myocytes and endothelial cells subjected to 15 minutes of ischaemia was not affected by the treatment of the fixative. However, when the tissue subjected to longer periods of ischaemia was fixed with routinely prepared or oxygen-bubbled glutaraldehyde, ultrastructural changes characteristic of reoxygenation damage were uniformly evident in both the microvasculature and myocytes. These qualitatively distinct changes included mitochondrial swelling, cell swelling, endothelial bleb formation, and narrowing of capillary lumina. These abnormalities were not observed in tissue fixed with nitrogen-bubbled glutaraldehyde. These findings indicate that deliberate steps should be taken to reduce or eliminate dissolved oxygen from the fixatives used to study ischaemic tissues. Otherwise artefactual reoxygenation damage in vitro may occur and make valid ultrastructural interpretation difficult or impossible.     

Revisiting the need for formal education in visualization.

Defining visualization education is still a work in progress. Visualization education is not just a subject within computer science. Computer scientists are not always the appropriate choice to teach visualization courses on their own. Visualization is not just mastering a set of concepts but acquiring skills. Student should learn by doing, either using one tool or a variety of tools, depending on the course's focus.     

On the complexity of simulating space-bounded quantum computations

This paper studies the space-complexity of predicting the long-term behavior of a class of stochastic processes based on evolutions and measurements of quantum mechanical systems. These processes generalize a wide range of both quantum and classical space-bounded computations, including unbounded error computations given by machines having algebraic number transition amplitudes or probabilities. It is proved that any space s quantum stochastic process from this class can be simulated probabilistically with unbounded error in space O(s), and therefore deterministically in space O(s²).     

The effect of solidification time and heat treatment on the fatigue properties of a cast 319 aluminum alloy

Solidification time and heat treatment are known to have a large effect on the microstructure of cast aluminum alloys. This study was conducted to quantify how the fatigue properties of a 319-type aluminum alloy are affected by solidification time and heat treatment. Both porosity-containing (non-hot isostatically pressed (HIP)) and porosity-free (HIP) samples in the T6 (“peak aged”) or T7 (“overaged”) heattreated conditions were tested. As the solidification time increased, the average initiating pore diameter increased and stress-controlled fatigue life decreased. Heat treatment was observed to have a large effect on fatigue properties of the HIP samples. However, in the non-HIP fatigue samples, heat treatment did not significantly change the fatigue life or fatigue strength of the cast 319-type alloy. The absence of an influence of heat treatment on fatigue response is attributed to the predominance of the microporosity in fatigue crack initiation in cast aluminum.     

Measurement of the Timoshenko Shear Stiffness. II: Effect of Transverse Compressibility

This is the second of two papers devoted to the issue of measuring the Timoshenko shear stiffness of thin-walled composite beams. In the first paper, the effect of warping on the effective Timoshenko shear stiffness, as measured through bending tests, was studied. The bending test was simulated using finite-element analysis, and the results indicated that the warping effect was minimal. On the other hand, the evidence suggests that transverse flexibility may have a significant influence on the effective Timoshenko shear stiffness, decreasing the effective shear stiffness at shorter test spans. The purpose of the present study is to further investigate this effect and to explore the use of a sandwich theory to predict the measurement error. A higher-order sandwich theory, which captures the transverse strain at concentrated loads and supports, is applied to a commercially available thin-walled composite beam. The results indicate that the sandwich model does capture the decrease in the effective shear stiffness at short spans, and the dependence of the shear stiffness on span-to-depth ratio is similar to that calculated in the first paper, using the finite-element method.