We investigate how nanospaces surrounded by a 10-membered ring of ZSM-5 zeolite affect the reaction intermediates formed during dioxygen activation by enclosed dicopper cations. Two types of dioxygen intermediates are considered: one is an O(2)...Cu(2) complex, where dioxygen binds to the two Cu cations, and the other is a bis(mu-oxo)dicopper complex converted from an O(2)...Cu(2) complex by the cleavage of the O-O bond. We employ large-scale density functional theory (DFT) calculations with the B3LYP functional to examine the energetics of the two dioxygen intermediates inside a 10-membered ring of ZSM-5 with double Si --> Al substitutions at variable locations. The properties of the O(2)...Cu(2) complexes, such as the dioxygen bridging modes and dioxygen activation, are strongly affected by the locations of the two Al atoms within the 10-membered ring. In particular, the O(2)...Cu(2) complexes have either end-on or side-on bridging modes depending on the substituted Al positions. On the other hand, the steric hindrances of a ZSM-5 cavity play crucial roles in determining the properties of the bis(mu-oxo)dicopper complexes containing a diamond Cu(2)O(2) core. By restricting its Cu(2)O(2) core to a 10-membered ring of ZSM-5 in which the two Al atoms are second-nearest neighbors, each Cu cation is tetrahedral four-coordinate. On the other hand, the Cu cations have almost square planar coordination inside a ZSM-5 where the Al atoms are fourth-nearest neighbors. The different Cu coordination environments are responsible for the different levels of stability; the planar diamond Cu(2)O(2) core is 30.7 kcal/mol more stable relative to the tetrahedral case. Since the ZSM-5 nanospaces directly influence the stability of the bis(mu-oxo)dicopper complexes by changing the Cu coordination environments, zeolite confinement effects on the bis(mu-oxo)dicopper complexes are more noticeable than those in the O(2)...Cu(2) cases. The DFT findings are important in terms of catalytic functions, because the spatial constraint from the ZSM-5 should significantly contribute to the stability of the reaction intermediates formed during the dioxygen activation.

The prevalence of DISH based on CT was 27.1%, which was higher than that of x-ray. In addition, intra- and inter-observer error by review of CT was less than that of x-ray. CT evaluation would be a better method for precise understanding of the state of DISH.

To investigate relationships between hemodynamic responses and neural activities in the somatosensory cortices, hemodynamic responses by near infrared spectroscopy (NIRS) and electroencephalograms (EEGs) were recorded simultaneously while subjects received electrical stimulation in the right median nerve. The statistical significance of the hemodynamic responses was evaluated by a general linear model (GLM) with the boxcar design matrix convoluted with Gaussian function. The resulting NIRS and EEGs data were stereotaxically superimposed on the reconstructed brain of each subject. The NIRS data indicated that changes in oxy-hemoglobin concentration increased at the contralateral primary somatosensory (SI) area; responses then spread to the more posterior and ipsilateral somatosensory areas. The EEG data indicated that positive somatosensory evoked potentials peaking at 22 ms latency (P22) were recorded from the contralateral SI area. Comparison of these two sets of data indicated that the distance between the dipoles of P22 and NIRS channels with maximum hemodynamic responses was less than 10 mm, and that the two topographical maps of hemodynamic responses and current source density of P22 were significantly correlated. Furthermore, when onset of the boxcar function was delayed 5-15 s (onset delay), hemodynamic responses in the bilateral parietal association cortices posterior to the SI were more strongly correlated to electrical stimulation. This suggests that GLM analysis with onset delay could reveal the temporal ordering of neural activation in the hierarchical somatosensory pathway, consistent with the neurophysiological data. The present results suggest that simultaneous NIRS and EEG recording is useful for correlating hemodynamic responses to neural activity.