An expanded and revised compilation on the reactivity of singlet oxygen, the lowest electronically excited singlet state of molecular oxygen, 1 O 2 *(1 ∆ g), in fluid solution is presented, which supersedes the publication of Wilkinson and Brummer, J. Phys. Chem. Ref. Data 10: 809 (1981). Rate constants for the chemical reaction and physical deactivation of singlet oxygen available through 1993 have been critically compiled. Solvent deactivation rates (k d) are tabulated for 145 solvents or solvent mixtures and second-order rate constants for interaction of singlet oxygen with 1915 compounds are reported.
Quenching of excited singlet and triplet states of many substances by ground state molecular oxygen produces singlet oxygen, the lowest electronically excited singlet state of molecular oxygen, 02e ag). The fractions of singlet and triplet states quenched which produce singlet oxygen and the quantum yields of formation of singlet oxygen in fluid solutions have been critically compiled. Methods for determining yield parameters have been reviewed. Data have been compiled from the literature through 1991. Photosensitizers such as aromatic hydrocarbons, aromatic ketones and thiones, quinones, coumarins, fluoresceins, transition metal complexes, and heterocyclics are included in Table 1. Porphyrins and phthalocyanines are included in Table 2. Other materials which have been investigated for singlet oxygen production, such as dyes and drugs, are collected in Table 3 along with heterogeneous systems such as polymer-bound photosensitizers.
Glass (Nature 1969;223:578-580) patterns are random dot stimuli that generate a percept of global structure. To study the mechanisms underlying this global form perception, concentric, radial, hyperbolic, and parallel Glass patterns were constructed. Thresholds for detecting each type of pattern were measured by degrading the patterns through the addition of noise. Concentric patterns yielded the lowest thresholds for all subjects, while radial and hyperbolic patterns produced somewhat higher thresholds. For all subjects the parallel patterns produced the highest thresholds. Threshold measurements as a function of the area containing pattern structure provided evidence for global pooling of orientation information in the detection of radial and concentric Glass patterns but only local pooling in the detection of parallel patterns. Monte-Carlo simulations demonstrate that plausible neural models can accurately predict the data. These models indicate that the visual system contains networks that pool orientation information within regions 3.5-4.5 degrees in diameter in central vision. This pooling is organized to extract cross-shaped, X-shaped, and quasi-circular forms from the retinal image. The results are in good agreement with recent single unit physiology of primate area V4, an intermediate level of the form vision pathway.
fMRI (functional magnetic resonance imaging) studies on humans have shown a cortical area, the fusiform face area, that is specialized for face processing. An important question is how faces are represented within this area. This study provides direct evidence for a representation in which individual faces are encoded by their direction (facial identity) and distance (distinctiveness) from a prototypical (mean) face. When facial geometry (head shape, hair line, internal feature size and placement) was varied, the fMRI signal increased with increasing distance from the mean face. Furthermore, adaptation of the fMRI signal showed that the same neural population responds to faces falling along single identity axes within this space.
A detailed and extended chemical mechanism describing tropospheric aqueous phase chemistry (147 species and 438 reactions) is presented here as Chemical Aqueous Phase Radical Mechanism (CAPRAM) 2.4 (MODAC mechanism). The mechanism based on the former version 2.3 [Herrmann et al., 2000] contains extended organic and transition metal chemistry and is formulated more explicitly based on a critical review of the literature. The aqueous chemistry has been coupled to the gas phase mechanism Regional Atmospheric Chemistry Modeling (RACM) [Stockwell et al., 1997], and phase exchange accounted for using the resistance model of Schwartz [1986]. A method for estimating mass accommodation coefficients (α) is described, which accounts for functional groups contained in a particular compound. A condensed version has also been developed to allow the use of CAPRAM 2.4 (MODAC mechanism) in higher‐scale models. Here the reproducibility of the concentration levels of selected target species (i.e., NOx, S(IV), H2O2, NO3, OH, O3, and H+) within the limits of ± 5% was used as a goal for eliminating insignificant reactions from the complete CAPRAM 2.4 (MODAC mechanism). This has been done using a range of initial conditions chosen to represent different atmospheric scenarios, and this produces a robust and concise set of reactions. The most interesting results are obtained using atmospheric conditions typical for an urban scenario, and the effects introduced by updating the aqueous phase chemistry are highlighted, in particular, with regard to radicals, redox cycling of transition metal ions and organic compounds. Finally, the reduced scheme has been incorporated into a one‐dimensional (1‐D) marine cloud model to demonstrate the applicability of this mechanism.
Humans are remarkably sensitive in detecting small deviations from circularity. In tasks involving discrimination between closed contours, either circular in shape or defined by sinusoidal modulations of the circle radius, human performance has been shown to be limited by global processing. We assessed the amount of global pooling for different pattern shapes (different radial modulation frequencies, RF) when circular deformation was restricted to a fraction of the contour. The results show that the improvement in performance depends on the modulation frequency (the pattern shape) when increasing the number of cycles of an RF pattern. Global processing only extends up to modulation frequencies between 5 and 10. For higher frequencies, performance can be predicted by probability summation. Position uncertainty cannot explain these effects. In a circumstance where global pooling exceeds probability summation (RF=5), we split the pattern up into five identical segments conserving the total amount of information presented. Thresholds are significantly affected by different global arrangements of these segments: (a) Occluding small parts of the pattern shows a significant effect on the position of occluders with performance lowest when gaps are placed at the points of maximum curvature. (b) Shifting segments away from the pattern centre (exploded condition) or displaying them out of concentric context (spiral condition) shuts down global processing. (c) Jittering segments radially disrupts both global and local processing. We conclude that RF patterns in the global processing range are analysed by detecting the points of maximum curvature and that, in this range, the visual system can only reliably process up to about 5 local curvature extrema.
Psychophysical data demonstrate that orientation information in concentric, random-dot Glass patterns is summed linearly to extract a global form percept. Surprisingly, no such global pooling was found for Glass patterns with parallel structure. A simple neural model explains these results and agrees with recent V4 single unit physiology. As V4 provides the major input to IT, global concentric units may play an important role in analyzing complex images such as faces. In support of this possibility, deficits in the perception of concentric Glass patterns have recently been linked to prosopagnosia.
The available rate data on the reactivity and physical deactivation of molecular oxygen in its first electronic excited state (1Δg) in liquid solution have been critically compiled. Where possible, relative rates reported in the literature have been normalized to standard values selected by a statistical analysis of the experimental data. Second order rate constants for the deactivation and chemical reaction of singlet oxygen are reported for 670 compounds. Additionally, psuedo first order rate constants (kd) for solvent deactivation of singlet oxygen are reported for 50 different solvents.
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