Kinetic hole burning, hole filling, and conformational relaxation in heme proteins: direct evidence for the functional significance of a hierarchy of dynamical processes

Band III is a disorder and conformation-sensitive near-infrared (approximately 760 nm) charge transfer absorption band characteristic of equilibrium and nonequilibrium five coordinate ferrous high-spin hemes. The time evolution of this absorption band subsequent to photodissociation of six coordinate ferrous hemoglobin or myoglobin can provide detailed information regarding conformational relaxation, including the thermally driven fluctuations that result in the transition from inhomogeneous to homogeneous ligand rebinding kinetic. Such time-resolved measurements over a range of temperatures are difficult due to long sample recovery times at cryogenic temperatures. A new restoring technique that allows for the rapid movement of a large optically accessible cryostat is used in combination with nanosecond time-resolved near-infrared absorption spectroscopy to generate band III as a function of time for the photoproducts of the carbon monoxide derivative of adult human hemoglobin (COHbA) and, to a more limited extent, horse myoglobin (COMb). The measurements are made over a wide range of temperatures extending from well below the solvent (75% glycerol:water) glass transition at approximately 180 K to ambient temperatures. Three temperature- and/or viscosity-dependent phenomena are observed. At the highest temperatures, only conformational relaxation is observed for the 75% glycerol sample. At very high viscosity (> or = 400 cp), conformational relaxation slows dramatically, and both kinetic hole burning followed by the filling in of the "hole" (dynamic hole filling) are observed. As the temperature is lowered, conformational relaxation slows and finally ceases. Kinetic hole burning and dynamic hole filling as well as additional broadening of band III are observed down to 140 K. The observation of kinetic hole burning (KHB) is indicative of the sample being inhomogeneous on the time scale of the ligand rebinding giving rise to KHB. The onset of hole filling is a direct manifestation of the thermal homogenization of the initial inhomogeneous distribution of conformational substates responsible for KHB. The observed dynamics are used to explain the inverse temperature effect associated with the non-Arrhenius slow down of geminate rebinding above approximately 180 K. The inverse temperature effect appears to arise not only from the onset of conformational relaxation but also from the increase in the rate on thermal averaging of the initial inhomogeneous distribution of conformational substates.     

Asymmetric spin-echo imaging of magnetically inhomogeneous systems: theory, experiment, and numerical studies

The ability of the asymmetric spin-echo (ASE) pulse sequence to provide different degrees of spin-echo (SE)-type and gradient-echo (GE)-type contrast when imaging media containing magnetic inhomogeneities is investigated. The dependence of the ASE signal on the size of magnetic field perturbers is examined using theory, computer simulations, and experiment. A theoretical prediction of the ASE signal is obtained using the Anderson-Weiss mean field theory, the results of which are qualitatively supported by computer simulations and experimental studies. It is shown that the ASE sequence can be used to tune the range of perturber sizes that provide the largest contributions to susceptibility contrast effects.     

Causal ordering of academic self-concept and academic achievement: A multiwave, longitudinal panel analysis.

There is surprisingly little sound research on the causal ordering of academic self-concept and academic achievement in longitudinal panel studies, despite its theoretical and practical significance. Data collected in Grades 10, 11, 12, and 1 yr after graduation from high school that were used in this study come from the large (N?=?1,456 students), nationally representative Youth in Transition study (e.g., J. G. Bachman; 1970). It was found that reported grade averages in Grades 11 and 12 were significantly affected by academic self-concept measured the previous year, whereas prior reported grades had no effect on subsequent measures of academic self-concept. The results provide one of the few defensible demonstrations of prior academic self-concept influencing subsequent academic achievement, and the study appears to be methodologically stronger than previous research. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

A neural theory of attentive visual search: Interactions of boundary, surface, spatial, and object representations.

Visual search data are given a unified quantitative explanation by a model of how spatial maps in the parietal cortex and object recognition categories in the inferotemporal cortex deploy attentional resources as they reciprocally interact with visual representations in the prestriate cortex. The model visual representations are organized into multiple boundary and surface representations. Visual search in the model is initiated by organizing multiple items that lie within a given boundary or surface representation into a candidate search grouping. These items are compared with object recognition categories to test for matches or mismatches. Mismatches can trigger deeper searches and recursive selection of new groupings until a target object is identified. The model provides an alternative to Feature Integration and Guided Search models. (PsycINFO Database Record (c) 2010 APA, all rights reserved)